Catalyst composition

ABSTRACT

This invention relates to catalyst compounds, catalysts systems and methods to oligomerize or polymerize monomers where the catalyst compound and the catalyst system comprise compounds of formula: LMX 2  or (LMX 2 ) 2  wherein: M is a Group 7, 8, 9, 10 or 11 transition metal; L is a tridentate or tetradentate neutrally charged ligand that is bonded to M by at least three nitrogen atoms; at least one of the nitrogen atoms is a central non-pyridinal nitrogen atom and is not bonded to its adjacent atoms by a multibond; at least two of the nitrogen atoms are terminal nitrogen atoms; at least one terminal nitrogen atom is part of a pyridinyl ring; at least one other terminal nitrogen atom is substituted with at least one C 3 -C 50  hydrocarbyl or halobydrocarbyl; the central nitrogen atom is bonded to at least two different carbon atoms; and each X is an anionic monodentate ligand.

This application is a divisional of U.S. Ser. No. 10/802,514, filed Mar.17, 2004, now issued U.S. Pat. No. 7,217,675, which claims priority toUnited Kingdom Application 0306418.5, filed Mar. 20, 2003, thedisclosures of which are incorporated by reference in their entireties.

FIELD OF THE INVENTION

This invention relates to late transition metal catalysts for olefinoligomerizations or polymerization and to methods for making and usingthese catalysts.

BACKGROUND OF THE INVENTION

Alpha-olefins, especially those containing 6 to 20 carbon atoms, areimportant items of commerce. They are used as intermediates in themanufacture of detergents, as monomers (especially in linear low-densitypolyethylene), and as intermediates for many other types of products.Consequently, improved methods of making these compounds are desired.Especially desired, is a process capable of making a range of linearα-olefins such as 1-butene and 1-hexene.

Most commercially produced alpha-olefins are made by the oligomerizationof ethylene, catalyzed by various types of compounds, see for instanceB. Elvers, et al., Ed. Ullmann's Encyclopedia of Industrial Chemistry,Vol. A13, VCH Verlagsgesellschaft mbH, Weinheim, 1989, p. 243-247 and275-276, and B. Cornils, et al., Ed., Applied Homogeneous Catalysis withOrganometallic Compounds, A Comprehensive Handbook, Vol. 1, VCHVerlagsgesellschaft mbH, Weinheim, 1996, p. 245-258. The major types ofcommercially used catalysts are alkylaluminum compounds, certainnickel-phosphine complexes, and a titanium halide with a Lewis acid. Inall of these processes, significant amounts of branched internal olefinsand diolefins are produced. Since in most instances these areundesirable and often difficult to separate, these byproducts areavoided commercially.

More recently, some iron complexes bearing tridentate chelatingbis(imino)pyridine ligands have been reported, produce oligomers whenactivated (B. L. Small and M. Brookhart, J. Am. Chem. Soc. 1998, 120,7143; M. Brookhart and B. L. Small, PCT Int. Appl. WO9902472, 1999(DuPont)). Imino-bipyridine based iron complexes when activated producelow molecular weight oligomers (G. J. P. Britovsek, S. D. Baugh, O.Hoarau, V. C. Gibson, D. F. Wass, A. J. P. White, D. J. Williams, Inorg.Chim. Acta 2003, 345, 279. Bis(hydrazone)pyridine complexes of ironafford mixtures of low molecular weight polymer and oligomers (G. J. P.Britovsek, V. C. Gibson, B. S. Kimberley, S. Mastroianni, C. Redshaw, G.A. Solan, A. J. P. White, D. J. Williams, J. Chem. Soc., Dalton Trans.2001, 1639; M. O. Kristen, A. Gonioukh, D. Lilge, S. Lehmann, B.Bildstein, C. Amort, M. Malaun PCT Int. Appl. WO0114391, 2001 (BASF); L.S. Moody, P. B. MacKenzie, C. M. Killian, G. G. Lavoie, J. A. PonasikJr., T. W. Smith, J. C. Pearson, A. G. M. Barrett, G. W. Coates, PCTInt. Appl. WO0183571, 2001 (Eastman); L. S. Moody, P. B. MacKenzie, C.M. Killian, G. G. Lavoie, J. A. Ponasik Jr., A. G. M. Barrett, T. W.Smith, J. C. Pearson, PCT Int. Appl. WO0050470, 2000 (Eastman)). Ironbased oligomerization catalysts have been reported in G. J. P.Britovsek, S. Mastroianni, G. A. Solan, S. P. D. Baugh, C. Redshaw, V.C. Gibson, A. J. P. White, D. J. Williams and M. Elsegood, Chem. Eur.J., 2000, 6, 221, and in G. J. Britovsek, B. Dorer, V. C. Gibson, B. S.Kimberley and G. A. Solan, WO9912981, 1999 (BP Chemicals Ltd.).

Hence new oligomerization catalysts are of great interest in theindustry because they offer many new opportunities for providing newprocesses and products in a cheaper and more efficient manner. Thefollowing invention relates to new oligomerization technology based uponnew late transition metal catalyst compounds.

SUMMARY OF THE INVENTION

The present invention is directed toward Group 7, 8, 9, 10, or 11transition metal compounds containing neutral tridentate or tetradentatenitrogen based ligands and an activator that are useful foroligomerizing or polymerizing olefins, particularly α-olefins, or otherunsaturated monomers. For purposes of this disclosure, “α-olefins”includes ethylene.

Catalyst components of this invention comprise transition metalcompounds (precatalyst or catalyst precursor) of formula: LMX₂ or(LMX₂)₂ wherein each M is, independently, a Group 7, 8, 9, 10 or 11metal, preferably a Group 7, 8, 9, or 10 metal; L is, independently, atridentate or tetradentate neutrally charged ligand that is bonded to Mby three or four nitrogen atoms, where at least one of the nitrogenatoms is a central nitrogen atom, and at least two of the nitrogen atomsare terminal nitrogen atoms, and at least one terminal nitrogen atom ispart of a pyridinyl ring, a different terminal nitrogen atom issubstituted with one C₃-C₅₀ hydrocarbyl and one hydrogen atom or twohydrocarbyls wherein at least one hydrocarbyl is a C₃-C₅₀ hydrocarbyl,and the central nitrogen atom is bonded to three different carbon atomsor two different carbon atoms, and one hydrogen atom; X is,independently a monoanionic ligand or, two X are joined together to forma bidentate dianionic ligand. “Independently” means that when two ormore of the substitutents are present, they may differ one from theother.

Accordingly, in one aspect of the present invention, a catalystprecursor comprises a compound represented by the formula: LMX₂ or theformula (LMX₂)₂ wherein each M is, independently, a Group 7, 8, 9, 10 or11 transition metal; L is, independently, a tridentate or tetradentateneutrally charged ligand that is bonded to M by at least three nitrogenatoms; at least one of the nitrogen atoms is a central nitrogen atom; atleast two of the nitrogen atoms are terminal nitrogen atoms; at leastone terminal nitrogen atom is part of a pyridinyl ring; at least oneother terminal nitrogen atom is substituted with at least one C₃-C₅₀hydrocarbyl; the central nitrogen atom is bonded to at least twodifferent carbon atoms; and X is, independently, an anionic monodentateligand or two X may join together to form a bidentate dianionic ligand.

This invention further relates to compositions or transition metalcompounds represented by formula 1:

wherein each M is, independently, a group 7, 8, 9, 10, or 11 transitionmetal; N is nitrogen; C is carbon; X is, independently, an anionicmonodentate ligand, or two X groups together form a bidentate dianionicligand; R′ is, independently, a hydrogen, a hydrocarbyl, a substitutedhydrocarbyl, a halocarbyl, or a substituted halocarbyl; orindependently, two R′ groups on the same carbon join to form a cyclic orpolycyclic ring structure; when x is 2, 3, or 4, and/or when y is 2, 3,or 4, two or more R′ groups on adjacent carbon atoms may join to form acyclic or polycyclic ring structure; x is, independently, 1, 2, 3 or 4;y is, independently, 1, 2, 3 or 4; R¹, R², R³ and R⁴ or, independently,a hydrogen, a hydrocarbyl, a substituted a hydrocarbyl, a halocarbyl, ora substituted halocarbyl, or independently, two adjacent R¹, R², R³ orR⁴ join together to form a cyclic or polycyclic ring structure; R⁵ is,independently, a hydrogen, hydrocarbyl or halocarbyl; R⁶ is,independently, a C₃ to C₅₀ hydrocarbyl or a C₃ to C₅₀ halocarbyl; R⁷ is,independently, hydrogen, a hydrocarbyl, a substituted hydrocarbyl, ahalocarbyl, or a substituted halocarbyl; R⁷ may be bonded to M throughthe heteroatom of a substituted hydrocarbyl or a substituted halocarbyl;L′ is a neutral ligand bonded to M; and w is 0 or 1.

Accordingly, in another aspect of the present invention is a catalystprecursor represented by formula 1, 2, 3, and/or 4, wherein M is a Group7, 8, 9, 10, or 11 transition metal; N is nitrogen; C is carbon; X is,independently, an anionic monodentate ligand, or both X groups togetherform a bidentate dianionic ligand; R′ is, independently, a hydrogen, ahydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substitutedhalocarbyl, a cyclic ring comprising two R′ groups on the same carbon, apolycyclic ring comprising two R′ groups on the same carbon, a cyclicring comprising two or more R′ groups on adjacent carbons, or apolycyclic ring comprising two or more R′ groups on adjacent carbons; xis 1, 2, 3, or 4; y is 1, 2, 3, or 4, R¹, R², R³ or R⁴ is,independently, a hydrogen, a hydrocarbyl, a substituted a hydrocarbyl, ahalocarbyl, a substituted halocarbyl, a cyclic ring structure comprisingtwo adjacent R¹, R², R³ or R⁴, or a polycyclic ring structure comprisingtwo adjacent R¹, R², R³ or R⁴; R⁵ is a hydrogen, a hydrocarbyl or ahalocarbyl; R⁶ is a C₃ to C₅₀ hydrocarbyl or a C₃ to C₅₀ halocarbyl; R⁷is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, asubstituted halocarbyl; a substituted hydrocarbyl comprising aheteroatom, wherein the heteroatom is bonded to M, or a substitutedhalocarbyl comprising a heteroatom, wherein the heteroatom is bonded toM; L′ is a neutral ligand bonded to M; and w is 0 or 1.

This invention further relates to a catalyst system comprising any oneof the above catalyst precursors and an activator, and a process tooligomerize and/or polymerize an unsaturated monomer using the catalystsystem described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the molecular structure of 3a.

FIG. 2 represents the molecular structure of 3b.

FIG. 3 represents the molecular structure of 4a.

FIG. 4 represents the molecular structure of 6c.

FIG. 5 represents the molecular structure of 7a.

FIG. 6 depicts the Schulz-Flory distribution for runs 3 and 4 usingpre-catalysts, 3c and 4c, respectively.

FIG. 7 depicts the oligomer distribution of oligomer fractions versuscarbon number for runs 3 and 4 using pre-catalysts 3c and 4c,respectively.

DEFINITIONS

As used herein, the new numbering scheme for the Periodic Table Groupsare used as in Chemical and Engineering News, 63(5), 27 (1985).

When a polymer is referred to as “comprising an olefin”, the olefinpresent in the polymer is the polymerized form of the olefin. Likewisewhen catalyst components are described as comprising neutral stableforms of the components, it is well understood by one of ordinary skillin the art, that the ionic form of the component is the form that reactswith the monomers to produce polymers. In the description herein thetransition metal catalyst compound may be described as a catalystprecursor, a pre-catalyst compound or a catalyst compound, and theseterms are used interchangeably. A catalyst system is a combination of atransition metal catalyst compound and an activator. An activator isalso interchangeably referred to as a cocatalyst.

The term “hydrocarbyl radical” is sometimes used interchangeably with“hydrocarbyl,” and encompasses C₁-C₅₀ radicals. These radicals can belinear, branched, or cyclic (including polycyclic). These radicals canbe saturated, partially unsaturated or fully unsaturated, and whencyclic, may be aromatic or non-aromatic.

In describing a ligand, a terminal nitrogen atom is a nitrogen atom thatis indirectly bonded to only one other nitrogen atom. A central nitrogenatom is a nitrogen atom that is indirectly bonded to two or more othernitrogen atoms. An example is illustrated below:

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been replaced with a heteroatom or with at least onefunctional group such as NR″₂, OR″, PR″₂, SR″, BR″₂, SiR″₃, GeR″₃ andthe like or where at least one non-hydrocarbon atom or group has beeninserted within the hydrocarbyl radical, such as O, S, NR″, PR″, BR″,SiR″₂, GeR″₂, and the like, where R″ is independently a hydrocarbyl orhalocarbyl radical. The functional group can be an organometalloidradical.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen orhalogen-containing group (e.g. F, Cl, Br, I).

Substituted halocarbyl radicals are radicals in which at least onehydrocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR″₂, OR″, PR″₂, SR″, BR″₂, SiR′_(′3),GeR″₃ and the like, or where at least one non-carbon atom or group hasbeen inserted within the halocarbyl radical such as O, S, NR″, PR″, BR″,SiR″₂, GeR″₂, and the like where R″ is independently a hydrocarbyl orhalocarbyl radical provided that at least one halogen atom remains onthe original halocarbyl radical. The functional group can be anorganometalloid radical.

In some embodiments, the hydrocarbyl radical is independently selectedfrom methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl,tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl,nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl,tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl,nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl,heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl,tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl,nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl,tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl,nonacosynyl, or triacontynyl isomers.

For this disclosure, when a radical is listed it indicates that radicaltype and all other radicals formed when that radical type is subjectedto the substitutions defined above. Alkyl, alkenyl and alkynyl radicalslisted include all isomers including where appropriate cyclic isomers.For example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl,tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls);pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1-ethylpropyl, and neopentyl (and analogous substitutedcyclobutyls and cyclopropyls); butenyl includes E and Z forms of1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl (andcyclobutenyls and cyclopropenyls).

Cyclic compounds having substitutions include all isomer forms, forexample, methylphenyl would include ortho-methylphenyl,meta-methylphenyl and para-methylphenyl; dimethylphenyl would include2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl,2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.

The term oligomer refers to compositions having 2-75 mer units and theterm polymer refers to compositions having 76 or more mer units. A “mer”is defined as a unit of an oligomer or polymer that originallycorresponded to the olefin(s) used in the oligomerization orpolymerization reaction. For example, the mer of polyethylene would beethylene.

Anionic monodentate ligands, also called abstractable ligands, areligands that are removed from the catalyst precursor to activate it.They are sometimes assigned the label X in this disclosure. X isindependently a hydride radical, hydrocarbyl radical, orhydrocarbyl-substituted organometalloid radical; or two X's areconnected and form a 3-to-50-atom metallacycle ring. Specifically, thismetallacycle ring may take the form of a bidentate dianionic ligand.

When Lewis-acid activators such as methylalumoxane, aluminum alkyls,alkylaluminum alkoxides or alkylaluminum halides that are capable ofdonating an X ligand, to the transition metal component are used, orwhen an ionic activator is capable of extracting X, one or more X, whichmay optionally be bridged to one another, may additionally beindependently selected from a halogen, alkoxide, aryloxide, amide,phosphide or other anionic ligand, provided that the resulting activatedcatalyst contains as least one M−H or M−C connection in which an olefincan insert.

When the pre-catalysts of this invention are drawn as dimeric species,two X may be independently a mono-anionic bridging ligand that is bondedto each M (e.g. —X).

In some structures, the ligand-metal connection is drawn with an arrowindicating that the electrons originally came from the ligand. Thisconnection may also be shown by drawing a solid or dashed line. Thesedepictions are interchangeable.

Alicyclic rings are aliphatic radicals that have a ring or cyclicstructure in which the ring portion may be saturated or unsaturated, butin which the ring portion may not be aromatic. “Alicyclic,” as definedin this document, is a subset of “hydrocarbyl.”

DETAILED DESCRIPTION OF THE INVENTION

This invention further relates to compositions or transition metalcompounds represented by formula 1:

whereineach M is, independently, a group 7, 8, 9, 10, or 11 transition metal,preferably a group 7, 8, 9 or 10 transition metal, preferably nickel,cobalt, iron or manganese;N is nitrogen;C is carbon;each X is, independently, a hydride, hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl, or both X groupstogether are a hydrocarbdiyl, halocarbdiyl, substituted hydrocarbdiyl,or substituted halocarbdiyl;additionally, X may independently be selected from halogens, alkoxide,aryloxide, amide, phosphide, or other anionic ligands when Lewis-acidactivators (such as methylalumoxane, aluminum alkyls, alkylaluminumalkoxides) or alkylaluminum halides (capable of donating a hydride,hydrocarbyl, substituted hydrocarbyl, halocarbyl or substitutedhalocarbyl X ligand to the transition metal component) are used, or whenan ionic activator is capable of extracting X, provided that theresulting activated catalyst contains as least one M−H or M−C bond intowhich an olefin can insert (one or more X may optionally bridge to oneanother, as well); each R′ is, independently, a hydrogen, or ahydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substitutedhalocarbyl, preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀ substitutedhydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀ substitutedhalocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ to C₁₀substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl; independently, two R′ groups on the same carbonmay join to form a C₃ to C₆₁ cyclic or polycyclic ring structure; when xis 2, 3, or 4, and/or when y is 2, 3, or 4, two or more R′ groups onadjacent carbon atoms may join to form a C₄ to C₆₂ cyclic or polycyclicring structure;x is, independently, 1, 2, 3 or 4, preferably, x is 1;y is, independently, 1, 2, 3 or 4, preferably, y is 2;each R¹, R², R³ and R⁴ is, independently, a hydrogen, or a hydrocarbyl,a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl,preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀ substitutedhydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀ substitutedhalocarbyl, more preferably a C₁ to C₂₀ hydrocarbyl, a C₁ to C₂₀substituted hydrocarbyl, a C₁ to C₂₀ halocarbyl, or a C₁ to C₂₀substituted halocarbyl, or independently, one or more adjacent R¹, R²,R³, R⁴ may join to form a cyclic or polycyclic ring structure; R¹ ispreferably selected from the group consisting of methyl, ethyl, and alllinear and cyclic isomers of propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, phenyl, dimethylphenyl,diethylphenyl, dipropylphenyl, naphthyl, anthracenyl, and othersubstitutents; R¹ is even more preferably, methyl, ethyl, isopropyl,tert-butyl, neopentyl, cyclohexyl, phenyl, 2,6-dimethylphenyl,2,6-diisopropylphenyl, 2,5-di-tert-butylphenyl, naphthyl, anthracenyl,adamantyl, and norbornyl;each R⁵ is, independently, a hydrogen, or a hydrocarbyl, or ahalocarbyl, preferably a C₁ to C₃₀ hydrocarbyl, or a C₁ to C₃₀halocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, or a C₁ to C₁₀halocarbyl;each R⁶ is, independently, a C₃ to C₅₀ hydrocarbyl, or a C₃ to C₅₀halocarbyl, preferably a C₃ to C₃₀ hydrocarbyl, or a C₃ to C₃₀halocarbyl, more preferably a C₃ to C₂₀ hydrocarbyl, or a C₃ to C₂₀halocarbyl;each R⁷ is, independently, a hydrogen, or a hydrocarbyl, a substitutedhydrocarbyl, a halocarbyl, or a substituted halocarbyl, preferably a C₁to C₃₀ hydrocarbyl, a C₁ to C₃₀ substituted hydrocarbyl, a C₁ to C₃₀halocarbyl or a C₁ to C₃₀ substituted halocarbyl, more preferably a C₁to C₁₀ hydrocarbyl, a C₁ to C₁₀ substituted hydrocarbyl, a C₁ to C₁₀halocarbyl or a C₁ to C₁₀ substituted halocarbyl; optionally R⁷ may bebound to M through the heteroatom of a substituted hydrocarbyl or asubstituted halocarbyl;L′ is a neutral ligand bonded to M and includes molecules such as butnot limited to diethyl ether, tetrahydrofuran, dimethylaniline,trimethylamine, tributylamine, trimethylphosphine, triphenylphosphinelithium chloride, ethylene, propylene, butene, octene, styrene, and thelike; andw is 0 or 1 and indicates the absence or presence of L′.In a preferred embodiment the halocarbyls are fluorocarbyls and thesubstituted halocarbyls are substituted fluorocarbyls.

In another preferred embodiment, this invention further relates tocompositions represented by the formula 5:

whereinM, N, R¹, R⁵, R⁶, R⁷, X, L′ and w are as previously defined.

To illustrate members of the transition metal catalyst compounds usefulin this invention, select any combination of the species listed in Table1.

R⁶ R′, R¹, R², R³, R⁴, R⁵, R⁷ X M L′ propyl hydrogen chloride cobaltdiethyl ether butyl methyl bromide manganese tetrahydrofuran pentylethyl iodide iron furan hexyl propyl methyl nickel thiofuran heptylbutyl ethyl copper chromane octyl pentyl propyl technetium isochromanenonyl hexyl butyl rhenium thiochromane decyl heptyl pentyl rutheniumthioisochromane undecyl octyl hexyl osmium quinuclidine dodecyl nonylheptyl rhodium benzofuran tridecyl decyl octyl iridium chromenetetradecyl undecyl nonyl palladium isobenzofuran octacosyl dodecyl decylplatinum isoquinoline nonacosyl tridecyl undecyl silver oxazoletriacontyl tetradecyl dodecyl gold phenanthridine cyclohexyl octacosyltridecyl pyran cyclopentyl nonacosyl tetradecyl pyridine cycloheptyltriacontyl pentadecyl quinoline cyclooctyl cyclohexyl hexadecylselenophene cyclodecyl cyclopentyl heptadecyl thiophene cyclododecylcycloheptyl octadecyl trimethylamine naphthyl cyclooctyl nonadecyltriethylamine phenyl cyclodecyl eicosyl tributylamine tolyl cyclododecylheneicosyl dimethylaniline benzyl naphthyl docosyl trimethylphosphinephenethyl phenyl tricosyl triphenylphosphine dimethylphenyl tolyltetracosyl ethylene trimethylphenyl benzyl pentacosyl propylenemethylphenyl phenethyl hexacosyl butene ethylphenyl dimethylphenylheptacosyl hexene diethylphenyl diethylphenyl octacosyl octenetriethylphenyl anthracenyl nonacosyl cyclohexene propylphenyl adamantyltriacontyl vinylcyclohexene dipropylphenyl norbornyl hydride benzenetripropylphenyl phenyl styrene methylethylphenyl benzyl methylstyrenedibutylphenyl phenethyl lithium chloride butylphenyl tolyl ammoniumchloride methoxy ethoxy propoxy butoxy dimethylamido diethylamidomethylethylamido phenoxy benzoxy allyl Both X joined methylideneethylidene propylidene tetramethylene pentamethylene hexamethylenebutadiene methylbutadiene dimethylbutadiene pentadiene methylpentadienedimethylpentadiene hexadiene methylhexadiene dimethylhexadiene

Preferred transition metal catalyst compounds include:

-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron dichloride,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]iron    dichloride,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]copper    dichloride,-   [N-2,4-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,4-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]iron    dichloride,-   [N-2,4-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,4-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]copper    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminopropyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminopropyl)(2-picolyl)amine]iron    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminopropyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminopropyl)(2-picolyl)amine]copper    dichloride,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]iron    dichloride,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]copper    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminopropyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminopropyl)(2-picolyl)amine]iron    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminopropyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminopropyl)(2-picolyl)amine]copper    dichloride,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt dichloride,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]iron dichloride,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]nickel dichloride,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]copper dichloride,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron dichloride,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4,6-trimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4,6-trimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4,6-trimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4,6-trimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4,6-triisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4,6-triisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4,6-triisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4,6-triisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4,6-trimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4,6-trimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4,6-trimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4,6-trimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4,6-triisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4,6-triisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4,6-triisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4,6-triisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]cobalt dichloride,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]iron dichloride,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]nickel dichloride,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]copper dichloride,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]cobalt    dichloride,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]iron    dichloride,-   [bis(2-picolyl)(N-2,4-dimethylphenyl-2-aminoethyl)amine]cobalt    dichloride,-   [bis(2-picolyl)(N-2,4-dimethylphenyl-2-aminoethyl)amine]iron    dichloride,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]cobalt    dichloride,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]iron    dichloride,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-(2,4,6-trimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-(2,4,6-trimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]cobalt    dichloride dimer,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]cobalt    dichloride dimer,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]iron    dichloride dimer,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]manganese    dichloride dimer,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dibromide,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron dibromide,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dibromide,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dibromide,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dibromide,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron dibromide,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dibromide,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dibromide,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dibromide,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dibromide,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dibromide,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dibromide,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dibromide,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dibromide,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dibromide,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dibromide,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dibromide,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dibromide,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dibromide,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dibromide,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]cobalt    dibromide,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]iron dibromide,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]nickel    dibromide,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]copper    dibromide,-   [N-2,4-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]cobalt    dibromide,-   [N-2,4-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]iron dibromide,-   [N-2,4-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]nickel    dibromide,-   [N-2,4-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]copper    dibromide,-   [N-2,4,6-trimethylphenyl-2-aminopropyl)(2-picolyl)amine]cobalt    dibromide,-   [N-2,4,6-trimethylphenyl-2-aminopropyl)(2-picolyl)amine]iron    dibromide,-   [N-2,4,6-trimethylphenyl-2-aminopropyl)(2-picolyl)amine]nickel    dibromide,-   [N-2,4,6-trimethylphenyl-2-aminopropyl)(2-picolyl)amine]copper    dibromide,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]cobalt    dibromide,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]iron    dibromide,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]nickel    dibromide,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]copper    dibromide,-   [N-2,4,6-triisopropylphenyl-2-aminopropyl)(2-picolyl)amine]cobalt    dibromide,-   [N-2,4,6-triisopropylphenyl-2-aminopropyl)(2-picolyl)amine]iron    dibromide,-   [N-2,4,6-triisopropylphenyl-2-aminopropyl)(2-picolyl)amine]nickel    dibromide,-   [N-2,4,6-triisopropylphenyl-2-aminopropyl)(2-picolyl)amine]copper    dibromide,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt dibromide,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]iron dibromide,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]nickel dibromide,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]copper dibromide,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt dibromide,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron dibromide,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]nickel dibromide,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]copper dibromide,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]dibromide    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4,6-trimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4,6-trimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4,6-trimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4,6-trimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4,6-triisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4,6-triisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4,6-triisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4,6-triisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4,6-trimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4,6-trimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4,6-trimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4,6-trimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4,6-triisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4,6-triisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4,6-triisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4,6-triisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4,6-trimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4,6-trimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4,6-trimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4,6-trimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-2,4,6-triisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-2,4,6-triisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-2,4,6-triisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dibromide,-   [N-2,4,6-triisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dibromide,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]cobalt dibromide,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]iron dibromide,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]nickel dibromide,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]copper dibromide,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dibromide,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dibromide,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dibromide,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dibromide,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]cobalt    dibromide,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]iron    dibromide,-   [bis(2-picolyl)(N-2,4-dimethylphenyl-2-aminoethyl)amine]cobalt    dibromide,-   [bis(2-picolyl)(N-2,4-dimethylphenyl-2-aminoethyl)amine]iron    dibromide,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]cobalt    dibromide,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]iron    dibromide,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [N-(2,4,6-trimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]iron    dibromide,-   [N-(2,4,6-trim    ethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]cobalt    dibromide,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]cobalt    dibromide dimer,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]cobalt    dibromide dimer,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]iron    dibromide dimer,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]manganese    dibromide dimer,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]rhodium    dichloride,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]ruthenium    dichloride,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]palladium    dichloride,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]silver    dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]rhodium    dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]ruthenium    dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]palladium    dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]silver    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]rhodium    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]ruthenium    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]palladium    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]silver    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]rhodium    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]ruthenium    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]palladium    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]silver    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]rhodium    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]ruthenium    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]palladium    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]silver    dichloride,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]rhodium    dichloride,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]ruthenium    dichloride,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]palladium    dichloride,-   [N-2,6-dimethylphenyl-2-aminopropyl)(2-picolyl)amine]silver    dichloride,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]rhodium    dichloride,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]ruthenium    dichloride,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]palladium    dichloride,-   [N-2,6-diisopropylphenyl-2-aminopropyl)(2-picolyl)amine]silver    dichloride,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]rhodium dichloride,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]ruthenium    dichloride,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]palladium    dichloride,-   [N-2-methylphenyl-2-aminoethyl)(2-picolyl)amine]silver dichloride,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]rhodium    dichloride,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]ruthenium    dichloride,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]palladium    dichloride,-   [N-2-isopropylphenyl-2-aminoethyl)(2-picolyl)amine]silver    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]rhodium    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]ruthenium    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]palladium    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]silver    dichloride,-   [N-2,4-dim    ethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]rhodium    dichloride,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]ruthenium    dichloride,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]palladium    dichloride,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]silver    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]rhodium    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]ruthenium    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]palladium    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]silver    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]rhodium    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]ruthenium    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]palladium    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]silver    dichloride,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]rhodium    dichloride,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]ruthenium    dichloride,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]palladium    dichloride,-   [N-2,6-dimethylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]silver    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]rhodium    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]ruthenium    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]palladium    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-isopropylpyrindi-2-ylmethyl)ethane-1,2-diamine]silver    dichloride,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]rhodium    dichloride,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]ruthenium    dichloride,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]palladium    dichloride,-   [N-2,6-dimethylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]silver    dichloride,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]rhodium    dichloride,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]ruthenium    dichloride,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]palladium    dichloride,-   [N-2,6-diisopropylphenyl-N-methyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]silver    dichloride,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]rhodium    dichloride,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]ruthenium    dichloride,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]palladium    dichloride,-   [N-2,6-dimethylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]silver    dichloride,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]rhodium    dichloride,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]ruthenium    dichloride,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]palladium    dichloride,-   [N-2,6-diisopropylphenyl-N-phenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]silver    dichloride,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]rhodium dichloride,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]ruthenium dichloride,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]palladium dichloride,-   [N-phenyl-2-aminoethyl)(2-picolyl)amine]silver dichloride,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]rhodium    dichloride,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]ruthenium    dichloride,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]palladium    dichloride,-   [N-2,6-diisopropyl-4-methylphenyl-2-aminoethyl)(2-picolyl)amine]silver    dichloride,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]rhodium    dichloride,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]ruthenium    dichloride,-   [bis(2-picolyl)(N-2,4-dimethylphenyl-2-aminoethyl)amine]rhodium    dichloride,-   [bis(2-picolyl)(N-2,4-dimethylphenyl-2-aminoethyl)amine]ruthenium    dichloride,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]rhodium    dichloride,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]ruthenium    dichloride,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]ruthenium    dibromide,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]rhodium    dibromide,-   [N-(2,4,6-trimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]ruthenium    dibromide,-   [N-(2,4,6-trimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]rhodium    dibromide,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]rhodium    dichloride dimer,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]rhodium    dichloride dimer,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]ruthenium    dichloride dimer, and-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]rhenium    dichloride dimer.

Most preferred transition metal complexes include:

-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron dichloride,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]nickel    dichloride,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]copper    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]nickel    dichloride,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]copper    dichloride,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]cobalt    dichloride,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]iron    dichloride,-   [bis(2-picolyl)(N-2,4-dimethylphenyl-2-aminoethyl)amine]cobalt    dichloride,-   [bis(2-picolyl)(N-2,4-dimethylphenyl-2-aminoethyl)amine]iron    dichloride,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]cobalt    dichloride,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]iron    dichloride,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [N-(2,4,6-trimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]iron    dichloride,-   [N-(2,4,6-trimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]cobalt    dichloride dimer,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]cobalt    dichloride dimer,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]iron    dichloride dimer, and-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]manganese    dichloride dimer.

Transition metal complexes of this invention are typically prepared byreacting the tridentate or tetradentate ligand, L, with the desiredmetal halide, preferably a metal dihalide, in an appropriate solvent,preferably n-butanol, and heating the reaction mixture.

Invention catalyst systems can additionally be prepared by combining, inany order, the ligand, with a Group 7, 8, 9, 10 or 11 metal halide salt,which may optionally be coordinated by solvent, in an activator solution(for example, methylalumoxane dissolved in toluene). All reactants maybe added in any order, or even essentially simultaneously.

Common activators that are useful with this invention include:

1. Alumoxanes including alkyl alumoxanes and modified alkylalumoxanes,such as methylalumoxane, modified methylalumoxane, ethylalumoxane andthe like;

2. Aluminum alkyls such as trimethyl aluminum, triethyl aluminum,triisopropyl aluminum and the like, and alkyl aluminum halides such asdiethyl aluminum chloride, and including alkylaluminum alkoxides; and

3. Ionizing or stoichiometric activators.

Alumoxane components useful as an activators typically are an oligomericaluminum compound represented by the general formula (R″—Al—O)n, whichis a cyclic compound, or R″(R″—Al—O)nAlR″2, which is a linear compound.In this general alumoxane formula, each R″ is independently a C1-C20alkyl radical, for example, methyl, ethyl, propyl, butyl, pentyl,isomers thereof, and the like, and “n” is an integer from 1-50. Mostpreferably, R″ is methyl and “n” is at least 4. Methylalumoxane and/ormodified methylalumoxanes are most preferred. Another preferredalumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A(commercially available from Akzo Chemicals, Inc. under the trade nameModified Methylalumoxane type 3A, U.S. Pat. No. 5,041,584). For furtherdescriptions see, EP 279586, EP 561476, WO94/10180 and U.S. Pat. Nos.4,665,208, 4,908,463, 4,924,018, 4,952,540, 4,968,827, 5,041,584,5,103,031, 5,157,137, 5,235,081, 5,248,801, 5,329,032, 5,391,793, and5,416,229.

Aluminum alkyl components useful as activators are represented by thegeneral formula: Rm′″AlZp

where each R′″ is, independently, a C₁-C₂₀ alkyl radical, for example,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, and isomers thereof, preferably methyl, ethyl,propyl, butyl, isobutyl, hexyl, octyl, more preferably methyl, ethyl,isobutyl, n-hexyl or n-octyl;m is 1, 2 or 3;each Z is, independently, a C₁-C₂₀ alkyl radical, for example, methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, and isomers thereof, preferably methyl, ethyl, propyl,butyl, isobutyl, hexyl, octyl, or n-octyl, each Z may also be adifferent univalent anionic ligand such as a halogen (preferably Cl, Br,I), or an alkoxide (OR*), where R* is a C₁-C₂₀ alkyl radical, forexample, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, and isomers thereof, preferably methyl,ethyl, propyl, butyl, isobutyl, hexyl, octyl, or n-octyl, preferably R*is preferably methyl, ethyl, propyl, butyl, isobutyl, hexyl, octyl,n-octyl, chloro, methoxide, ethoxide, propoxide, isopropoxide, butoxide,or t-butoxide; andp is 0, 1 or 2. Preferred aluminum alkyl compounds which may be utilizedas activators (or scavengers) include triethylaluminum, diethylaluminumchloride, triisobutylaluminum, tri-n-octylaluminum, trimethylaluminum,and tri-n-hexylaluminum.

When alumoxane, or aluminum alkyl activators are used, thecatalyst-precursor-to-activator molar ratio is preferably from about1:2000 to 10:1; alternatively, 1:1200 to 1:1; alternatively, 1:1000 to1:1; alternatively 1:500 to 1:1; alternatively 1:400 to 1:10, oralternatively 1:300 to 1:10.

Ionizing activators may be used in the practice of this invention.Preferably, discrete ionizing activators (sometimes also referred to asionic activators) such as [Me₂PhNH][B(C₆F₅)₄], [Bu₃NH][BF₄], [NH₄][PF₆],[NH₄][SbF₆], [NH4][AsF6], [NH4][B(C6H5)4] or Lewis acidic activatorssuch as B(C6F5)₃ or B(C₆H₅)₃ can be used if they are used in conjunctionwith a compound capable of alkylating the metal such as an alumoxane oraluminum alkyl, or if in the pre-catalyst, X is a hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl. Forpurposes of this invention and the claims thereto, Ph is phenyl, Bu isbutyl, C₆H₅ is phenyl; C₆F₅ is perfluorophenyl or pentafluorophenyl.

An ionizing or stoichiometric activator may be used, neutral or ionic,such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)boron, atris(perfluorophenyl)boron metalloid precursor or atris(perfluoronaphthyl)boron metalloid precursor, polyhalogenatedheteroborane anions (see WO 98/43983), boric acid (see U.S. Pat. No.5,942,459) or combination thereof. Neutral or ionizing activators mayalso be used alone or in combination with alumoxane or modifiedalumoxane activators.

Examples of neutral stoichiometric activators include: tri-substitutedboron, tellurium, aluminum, gallium and indium or mixtures thereof. Thethree substitutent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds, and mixtures thereof.

Preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groupshaving 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms,and aryl groups having 3 to 20 carbon atoms (including substitutedaryls). More preferably, the three groups are alkyls having 1 to 4carbon groups, phenyl, naphthyl or mixtures thereof. Even morepreferably, the three groups are halogenated aryl groups, preferablyfluorinated aryl groups. Most preferably, the neutral stoichiometricactivator is tris(perfluorophenyl)boron or tris(perfluoronaphthyl)boron.

Ionizing stoichiometric activator compounds may contain an activeproton, or some other cation associated with, but not coordinated to, oronly loosely coordinated to, the remaining ion of the ionizing compound.Such compounds and the like are described in European publicationsEP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401,5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

Ionic catalysts can be prepared by reacting a transition metal compoundwith one or more neutral Lewis acids, such as B(C₆F₆)₃, which uponreaction with the hydrolyzable ligand (X) of the transition metalcompound forms an anion, such as ([B(C₆F₅)3(X)]—), which stabilizes thecationic transition metal species generated by the reaction. Thecatalysts can be, and preferably are, prepared with activator componentswhich are ionic compounds or compositions. However preparation ofactivators utilizing neutral compounds is possible.

Compounds useful as an activator component in the preparation of theionic catalyst systems may also comprise a cation, which is preferably aBronsted acid capable of donating a proton, and a compatiblenon-coordinating anion which anion is relatively large (stericallybulky), capable of stabilizing the active catalyst species which isformed when the two compounds are combined, and said anion will besufficiently labile to be displaced by olefinicm, diolefinic andacetylenically unsaturated substrates or other neutral Lewis bases suchas ethers, nitriles and the like. Two classes of compatiblenon-coordinating anions are (as disclosed in EPA 277,003 and EPA 277,004published 1988: 1. anionic coordination complexes comprising a pluralityof lipophilic radicals covalently coordinated to and shielding a centralcharge-bearing metal or metalloid core, and 2. anions comprising aplurality of boron atoms such as carboranes, metallacarboranes andboranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:(L*-H)_(d) ⁺(A^(d−))  (14)wherein L* is an neutral Lewis base;H is hydrogen;(L*-H)⁺ is a Bronsted acidA^(d−) is a non-coordinating anion having the charge d−d is an integer from 1 to 3.

The cation component, (L*-H)d+ may include Bronsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from thetransition metal catalyst compound, resulting in a cationic transitionmetal species.

The activating cation (L*-H)d+ may be a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, and phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof. The activating cation (L-H)d+ may also be a moietysuch as silver, tropylium, carbeniums, ferroceniums and mixturesthereof, preferably carboniums and ferroceniums. Most preferably(L*-H)d+ is triphenyl carbonium.

The anion component Ad− includes those having the formula [Mk+Qn]d−wherein k is an integer from 1 to 3; n is an integer from 2-6; n−k=d; Mis an element selected from Group 13 of the Periodic Table of theElements, preferably boron or aluminum, and Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, or halosubstituted-hydrocarbyl radical, said Q having up to20 carbon atoms with the proviso that not more than one Q group is ahalide. Preferably, each Q is a fluorinated hydrocarbyl group having 1to 20 carbon atoms, more preferably each Q is a fluorinated aryl group,and most preferably each Q is a pentafluoryl aryl group. Examples ofsuitable Ad− also include diboron compounds as disclosed in U.S. Pat.No. 5,447,895, which is fully incorporated herein by reference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst (activator) include: trimethylammoniumtetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylaniliniumtetraphenylborate,

N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,di(isopropyl)ammonium tetraphenylborate, dicyclohexylammoniumtetraphenylborate; tri(o-tolyl)phosphonium tetraphenylborate,tri(2,6-dimethylphenyl)phosphonium tetraphenylborate, trimethylammoniumtetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate,di(isopropyl)ammonium tetrakis(pentafluorophenyl)borate,dicyclohexylammonium tetrakis(pentafluorophenyl)borate;tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,di(isopropyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,dicyclohexylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate;tri(o-tolyl)phosphonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,tri(2,6-dimethylphenyl)phosphoniumtetrakis(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate,di(isopropyl)ammonium tetrakis(pentafluoronaphthyl)borate,dicyclohexylammonium tetrakis(pentafluoronaphthyl)borate;tri(o-tolyl)phosphonium tetrakis(pentafluoronaphthyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluoronaphthyl)borate,trimethylammonium tetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate,di(isopropyl)ammonium tetrakis(pentafluorobiphenyl)borate,dicyclohexylammonium tetrakis(pentafluorobiphenyl)borate;tri(o-tolyl)phosphonium tetrakis(pentafluorobiphenyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorobiphenyl)borate,trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(t-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,di(isopropyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,dicyclohexylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;tri(o-tolyl)phosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,and tri(2,6-dimethylphenyl)phosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

Most preferably, the ionic stoichiometric activator (L*-H)d+(Ad−)comprises one or more of:

N,N-dimethylanilinium tetra(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetra(perfluorophenyl)borate.

One embodiment includes an activation method using ionizing ioniccompounds not containing an active proton, but capable of producing aligand metallocene catalyst cation, and their non-coordinating anion.These are described in EP-A-0 426 637, EP-A-0 573 403 and U.S. Pat. No.5,387,568, which are all herein incorporated by reference.

Invention catalyst precursors can also be activated with cocatalysts oractivators that comprise non-coordinating anions containingmetalloid-free cyclopentadienide ions. These are described in U.S.Patent Publication 2002/0058765 A1, published on 16 May 2002.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to said cation or which is only weakly coordinated tosaid cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substitutentor fragment to the cation so as to cause it to form a neutral fourcoordinate metallocene compound and a neutral by-product from the anion.Non-coordinating anions include those that are compatible, stabilize themetallocene cation in the sense of balancing its ionic charge at +1, yetretain sufficient liability to permit displacement by an ethylenically,or acetylenically unsaturated monomer during polymerization. These typesof cocatalysts sometimes use tri-isobutyl aluminum or tri-octyl aluminumas a scavenger.

Cocatalyst compounds or activator compounds may also be initiallyneutral Lewis acids, but form a cationic metal complex and anoncoordinating anion, or a zwitterionic complex upon reaction with theinvention compounds. For example, tris(pentafluorophenyl)boron oraluminum act to abstract a hydrocarbyl or hydride ligand to yield aninvention cationic metal complex and stabilizing noncoordinating anion.(See EP-A-0 427 697 and EP-A-0 520 732 for illustrations of analogousGroup-4 metallocene compounds.) Also, see the methods and compounds ofEP-A-0 495 375. For formation of zwitterionic complexes using analogousGroup 4 compounds, see U.S. Pat. Nos. 5,624,878; 5,486,632; and5,527,929.

When the cations of noncoordinating anion precursors are Bronsted acidssuch as protons or protonated Lewis bases (excluding water), orreducible Lewis acids such as ferrocenium or silver cations, or alkalior alkaline earth metal cations such as those of sodium, magnesium orlithium, the catalyst-precursor-to-activator molar ratio may be anyratio. Combinations of the described activator compounds may also beused for activation. For example, tris(perfluorophenyl)boron can be usedwith methylalumoxane.

When an ionic activator is used, the catalyst-precursor-to-activatormolar ratio is from 1:10 to 1.2:1; 1:10 to 10:1; 1:10 to 2:1; 1:10 to3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to 2:1; 1:3 to 3:1; 1:3 to 5:1;1:5 to 1.2:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to 3:1; 1:5 to 5:1.

The catalyst-precursor-to-alkylating-agent molar ratio is from 1:100 to100:1; 1:50 to 50:1; 1:10 to 10:1; 1:10 to 2:1; 1:10 to 25:1; 1:10 to3:1; 1:10 to 5:1; 1:2 to 10:1; 1:2 to 2:1; 1:2 to 25:1; 1:2 to 3:1; 1:2to 5:1; 1:25 to 10:1; 1:25 to 2:1; 1:25 to 25:1; 1:25 to 3:1; 1:25 to5:1; 1:3 to 10:1; 1:3 to 2:1; 1:3 to 25:1; 1:3 to 3:1; 1:3 to 5:1; 1:5to 10:1; 1:5 to 2:1; 1:5 to 25:1; 1:5 to 3:1; 1:5 to 5:1.

Preferred activators include methylalumoxane, modified methylalumoxane,and mixtures of methylalumoxane with dimethylaniliniumtetrakis(pentafluorophenyl)borate or tris(pentafluorophenyl)boron.

Preferred catalyst compound/activator combinations include:

-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride/methylalumoxane,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride/methylalumoxane,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride/methylalumoxane,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride/methylalumoxane,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride/methylalumoxane,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride/methylalumoxane,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride/methylalumoxane,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride/methylalumoxane,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/methylalumoxane,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/methylalumoxane,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/methyl alum oxane,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/methylalumoxane,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/methylalumoxane,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/methylalumoxane,-   [N-2,6-isopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/methyl alum oxane,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/methylalumoxane,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/methylalumoxane,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/methylalumoxane,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride/methylalumoxane,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride/methylalumoxane,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]cobalt    dichloride/methylalumoxane,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]iron    dichloride/methylalumoxane,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]cobalt    dichloride/methylalumoxane-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]iron    dichloride/methylalumoxane,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/methylalumoxane,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/methylalumoxane,-   [N-(2,4,6-trimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/methylalumoxane,-   [N-(2,4,6-trimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/methylalumoxane,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]cobalt    dichloride dimer/methylalumoxane,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]iron    dichloride dimer/methylalumoxane,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]cobalt    dichloride dimer/methylalumoxane,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]iron    dichloride dimer/methylalumoxane,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]manganese    dichloride dimer/alumoxane,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride/modified methylalumoxane,-   [N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride/modified methylalumoxane,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride/modified methylalumoxane,-   [N-2,4-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride/modified methylalumoxane,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride/modified methylalumoxane,-   [N-2,6-diisopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride/modified methylalumoxane,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride/modified methylalumoxane,-   [N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride/modified methylalumoxane,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/modified methylalumoxane,-   [N-2,6-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/modified methylalumoxane,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/modified methylalumoxane,-   [N-2,4-dimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/modified methylalumoxane,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/modified methyl alum oxane,-   [N-2,4,6-trimethylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/modified methylalumoxane,-   [N-2,6-isopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/modified methylalumoxane,-   [N-2,6-diisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/modified methylalumoxane,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/modified methylalumoxane,-   [N-2,4,6-triisopropylphenyl-N-(6-methylpyrindi-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/modified methylalumoxane,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt    dichloride/modified methylalumoxane,-   [N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron    dichloride/modified methylalumoxane,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]cobalt    dichloride/modified methylalumoxane,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]iron    dichloride/modified methylalumoxane,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]cobalt    dichloride/modified methylalumoxane-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]iron    dichloride/modified methylalumoxane,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/modified methylalumoxane,-   [N-(2,6-dimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/modified methylalumoxane,-   [N-(2,4,6-trimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]iron    dichloride/modified methylalumoxane,-   [N-(2,4,6-trimethylphenyl)-N,N-bis(6-methylpyridin-2-ylmethyl)ethane-1,2-diamine]cobalt    dichloride/modified methylalumoxane,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]cobalt    dichloride dimer/modified methylalumoxane,-   [bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine]iron    dichloride dimer/modified methylalumoxane,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]cobalt    dichloride dimer/modified methylalumoxane,-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]iron    dichloride dimer/modified methylalumoxane, and-   [bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine]manganese    dichloride dimer/modified alumoxane,    Mixed Catalysts

Mixed catalyst systems can also be used, for example, the inventioncatalyst can be used in conjunction with a second catalyst in the samereactor or in a series of reactors where the invention catalyst producesethylene oligomers and the second catalyst incorporates these oligomersinto a polymer backbone as a copolymer with ethylene.

Catalyst systems can comprise additional olefin polymerizationcatalysts. These additional olefin polymerization catalysts are any ofthose well known in the art to catalyze the olefin to polyolefinreaction. Some invention catalysts systems include Group-4-6metallocenes as additional olefin polymerization catalysts. Metallocenesinclude (un)bridged compounds containing one(mono(cyclopentadienyl)metallocenes) or two(bis(cyclopentadienyl)metallocenes) (un)substituted cyclopentadienylligand(s). In bridged metallocenes, a single, cyclopentadienyl ligandconnects to a heteroatom ligand with both coordinating to the metalcenter, or two cyclopentadienyl ligands connect together with bothcyclopentadienyl ligands coordinating to the metal center. Typicalcatalysts and their precursors are well known in the art. Suitabledescription appears in the patent literature, for example U.S. Pat. Nos.4,871,705, 4,937,299, 5,324,800, EP-A-0418044, EP-A-0591756,WO-A-92/00333 and WO-A-94/01471. Some embodiments select the metallocenecompounds from mono- or bis-cyclopentadienyl-substituted, Group-4, -5,and -6 metals in which cyclopentadienyls are (un)substituted with one ormore groups or are bridged to each other or to a metal-coordinatedheteroatom. Some embodiments select similar metallocene compounds exceptthey are not necessarily bridged to each other or to a metal-coordinatedheteroatom. See U.S. Pat. Nos. 5,278,264 and 5,304,614.

Some invention catalysts systems include the following additional olefinpolymerization catalysts. Metallocene compounds suitable for linearpolyethylene or ethylene-containing copolymer production (wherecopolymer means comprising at least two different monomers) areessentially those disclosed in WO-A-92/00333, WO 97/44370 and U.S. Pat.Nos. 5,001,205, 5,057,475, 5,198,401, 5,304,614, 5,308,816 and5,324,800. Selection of metallocene compounds for isotactic orsyndiotactic polypropylene blend production, and their syntheses, arewell-known in the patent and academic literature, e.g. Journal ofOrganometallic Chemistry 369, 359-370 (1989). Typically, those catalystsare stereorigid, asymmetric, chiral, or bridged-chiral metallocenes.Invention activators are suited for activating these types of catalystprecursors.

Likewise, some invention catalysts systems include the followingadditional olefin polymerization catalysts: monocyclopentadienylmetallocenes with Group-15 or -16 heteroatoms connected, through abridging group, to a cyclopentadienyl-ligand ring carbon. Both thecyclopentadienyl Cp-ligand and the heteroatom connect to a transitionmetal. Some embodiments select a Group-4 transition metal. Additionally,unbridged monocyclopentadienyl, heteroatom-containing Group-4 componentsof WO 97/22639 will function with this invention. Moreover, transitionmetal systems with high-oxidation-state, Group-5-10 transition-metalcenters are known and can serve as the additional olefin polymerizationcatalysts with invention catalyst systems.

Invention catalyst systems can use non-cyclopentadienyl, Group-4-5precursor compounds as the additional olefin polymerization catalysts.Non-cyclopentadienyl, Group-4-5 precursor compounds that are activableto stable, discrete cationic complexes include those containingchelating, diamide ligands, such as described in U.S. Pat. No.5,318,935, and “Conformationally Rigid Diamide Complexes Synthesis andStructure of Tantalum (III) Alkyne Derivatives”, D. H. McConville, etal, Organometallics 1995, 14, 3154-3156. U.S. Pat. No. 5,318,935describes bridged and unbridged, bis-amido catalyst compounds of Group-4metals capable of α-olefins polymerization. Bridged bis(arylamido)Group-4 compounds for olefin polymerization are described by D. H.McConville, et al., in Organometallics 1995, 14, 5478-5480. Syntheticmethods and compound characterization are described. Further workappearing in D. H. McConville, et al, Macromolecules 1996, 29,5241-5243, describes bridged bis(arylamido) Group-4 compounds that arepolymerization catalysts for 1-hexene. Additional invention-suitabletransition-metal compounds include those described in WO 96/40805.Cationic Group-3- or Lanthanide olefin polymerization complexes aredisclosed in copending U.S. application Ser. No. 09/408,050, filed 29Sep. 1999, and its equivalent PCT/US99/22690. Other suitable Group-4-5non-metallocene catalysts are bimetallocyclic catalyst compoundscomprising two independently selected Group-4-5 metal atoms directlylinked through two bridging groups to form cyclic compounds.

Invention catalyst systems can use other transition metal catalystprecursors that have a 2+ oxidation state as the additional olefinpolymerization catalyst. Typical Ni₂ ⁺ and Pd₂ ⁺ complexes are diimines,see “New Pd(II)- and Ni(II)-Based Catalysts for Polymerization ofEthylene and α-Olefins”, M. Brookhart, et al, J. Am. Chem. Soc., 1995,117, 6414-6415, WO 96/23010 and WO 97/02298. See additionally therelated bis(imino) Group-8 and -9 organometallic compounds described byV. C. Gibson and others in “Novel olefin polymerization catalysts basedon iron and cobalt”, Chem. Commun., 849-850, 1998.

For a review of other potential catalysts used in combination or serieswith the invention catalysts, see S. D. Ittel and L. K. Johnson, Chem.Rev. 2000, 1000, 1169 and V. C. Gibson and S. K. Spitzmesser, Chem. Rev.2003, 103, 283.

Some catalyst systems of this invention can produce greater than 95%linear α-olefins.

Supports

The transition metal catalyst components described herein may besupported. For example, one or more transition metal catalyst componentsand/or one or more activators may be deposited on, contacted with,vaporized with, bonded to, or incorporated within, adsorbed or absorbedin, or on, one or more supports or carriers.

The support material may be any of the conventional support materials.Preferably the support material is a porous support material, forexample, talc, inorganic oxides and inorganic chlorides. Other supportmaterials include resinous support materials such as polystyrene,functionalized or crosslinked organic supports, such as polystyrenedivinyl benzene polyolefins or polymeric compounds, zeolites, clays, orany other organic or inorganic support material and the like, ormixtures thereof.

Preferred support materials are inorganic oxides that include thoseGroup 2, 3, 4, 5, 13 or 14 metal oxides. Preferred supports includesilica, which may or may not be dehydrated, fumed silica, alumina (WO99/60033), silica-alumina and mixtures thereof. Other useful supportsinclude magnesia, titania, zirconia, magnesium chloride (U.S. Pat. No.5,965,477), montmorillonite (European Patent EP-B1 0 511 665),phyllosilicate, zeolites, talc, clays (U.S. Pat. No. 6,034,187) and thelike. Also, combinations of these support materials may be used, forexample, silica-chromium, silica-alumina, silica-titania and the like.Additional support materials may include those porous acrylic polymersdescribed in EP 0 767 184 B1, which is incorporated herein by reference.Other support materials include nanocomposites as described in PCT WO99/47598, aerogels as described in WO 99/48605, spherulites as describedin U.S. Pat. No. 5,972,510 and polymeric beads as described in WO99/50311, which are all herein incorporated by reference. Lewis acidicmaterials such as montmorillonite and similar clays may also serve as asupport. In this case, the support can optionally double as theactivator component. But additional activator may also be used.

Preferably the support material, most preferably an inorganic oxide, hasa surface area in the range of from about 10 to about 700 m2/g, porevolume in the range of from about 0.1 to about 4.0 cc/g, and averageparticle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m2/g, pore volume of from about 0.5 to about3.5 cc/g, and average particle size of from about 10 to about 200 μm.Most preferably the surface area of the support material is in the rangeis from about 100 to about 400 m2/g, pore volume from about 0.8 to about3.0 cc/g, and average particle size is from about 5 to about 100 μm. Theaverage pore size of the carrier typically has pore size in the range offrom 10 to 1000 Å, preferably 50 to about 500 Å, and most preferably 75to about 350 Å.

As is known in the art, the catalysts may also be supported together onone inert support, or the catalysts may be independently placed on twoinert supports and subsequently mixed. Of the two methods, the former ispreferred.

In another embodiment the support may comprise one or more types ofsupport material which may be treated differently. For example one coulduse two different silicas that have different pore volumes or have beencalcined at different temperatures. Likewise one could use a silica thathas been treated with a scavenger or other additive, and with a silicathat has not been treated.

Supported transition metal catalyst compounds, activators, or catalystsystems may be prepared by placing the support material (which may bepre-treated, such as calcined or functionalized) and one or morecatalyst compounds, or one or more activators, or both activators andcatalyst compounds in a diluent, typically a solvent, and them removingthe diluent or solvent. The volume of the liquid may be from 0.5 to 20time the pore volume of the support or more. Certain embodiments,however, use 1 to 3 times the pore volume of the support or less than 1times the pore volume of the support.

Typically supported catalyst systems are prepared by methods effectiveto support other coordination catalyst systems, effective meaning thatthe catalyst so prepared can be used for oligomerizing or polymerizingmonomers in a heterogeneous process. The catalyst precursor, activator,suitable diluent, and support may be added in any order orsimultaneously. In one invention embodiment, the activator, dissolved inan appropriate solvent such as toluene is stirred with the supportmaterial for 1 minute to 10 hours. The total volume of the activationsolution may be greater than the pore volume of the support, but someembodiments limit the total solution volume below that needed to form agel or slurry (about 100-200% of the pore volume). In some embodimentsthe volume of the solution is limited to between 1 and 5 times the porevolume of the support, typically between 1.5 and 3. The mixture isoptionally heated to 30-200° C. during this time. The catalyst can beadded to this mixture as a solid, if a suitable solvent is employed inthe previous step, or as a solution. Or alternatively, this mixture canbe filtered, and the resulting solid mixed with a catalyst precursorsolution. Similarly, the mixture may be vacuum dried and mixed with acatalyst precursor solution. The resulting catalyst mixture is thenstirred for 1 minute to 10 hours, and the catalyst is either filteredfrom the solution and vacuum dried, or vacuum or evaporation aloneremoves the solvent.

In another invention embodiment, the catalyst precursor and activatorare combined in solvent to form a solution. The support is then added tothis solution and the mixture is stirred for 1 minute to 10 hours. Thetotal volume of this solution may be greater than the pore volume of thesupport, but some embodiments limit the total solution volume below thatneeded to form a gel or slurry (about 100-200% pore volume). In someembodiments the volume of the solution is limited to between 1 and 5times the pore volume of the support, typically between 1.5 and 3. Theresidual solvent is then removed, typically under vacuum, typically atambient temperature and over 10-16 hours. But greater or lesser timesare possible.

The catalyst precursor may also be supported in the absence of theactivator, in which case the activator may be added to the liquid phaseof a slurry process. For example, a solution of catalyst precursor maybe mixed with support material for a period of up to 10 hours. Theresulting catalyst precursor mixture is then filtered from the solutionand dried under vacuum, or vacuum or evaporation alone removes thesolvent. The total volume of the catalyst precursor solution may begreater than the pore volume of the support, but some embodiments limitthe total solution volume below that needed to form a gel or slurry(about 100-200% of the pore volume). In some embodiments the volume ofthe solution is limited to between 1 and 5 times the pore volume of thesupport, typically between 1.5 and 3. Additionally, two or moredifferent catalyst precursors may be placed on the same support usingany of the support methods disclosed above. Likewise, two or moreactivators may be placed on the same support.

As is well know in the art, the support material may be pretreated byany number of methods. For example, inorganic oxides may be calcined,and/or chemically treated with dehydroxylating agents such as aluminumalkyls and the like.

Some embodiments select the carrier of invention catalysts to have asurface area of 10-700 m2/g, or pore volume of 0.1-4.0 cc/g, and averageparticle size from 10-500 microns. But greater or lesser values may alsobe used.

The transition metal catalyst compounds may generally be deposited onthe support at a loading level of 10-100 micromoles of catalystprecursor per gram of solid support; alternately from 20-80 micromolesof catalyst precursor per gram of solid support; or from 40-60micromoles of catalyst precursor per gram of support. But greater orlesser values may be used. Some embodiments select greater or lesservalues, but require that the total amount of solid catalyst precursordoes not exceed the support's pore volume.

Additionally, oxidizing agents may be added to the supported orunsupported catalyst as described in WO 01/68725.

In another embodiment the activator is bound to the support prior tocombination with the transition metal catalyst compound. For moreinformation on support bound activators, see U.S. Pat. No. 5,643,847,U.S. Pat. No. 5,972,823, EP 0 775 164 B1, WO 00/4059 A1, and WO 95/9578A1.

Oligomerization or Polymerization Process

The catalyst compositions described above may be used to oligomerize orpolymerize any unsaturated monomer, however they are preferably used tooligomerize olefins, typically alpha-olefins. In the instantoligomerization processes, the process temperature is preferably from−100° C. to 300° C., −20° C. to 200° C., or 0° C. to 150° C. Someembodiments select oligomerization pressures (gauge) from 0 kPa-35 MPaor 500 kPa-15 MPa. A preferred feedstock for the oligomerization processis the alpha-olefin, ethylene. But other alpha-olefins, including butnot limited to propylene and 1-butene, may also be used alone orcombined with ethylene. Preferred alpha-olefins include any C₂ to C₄₀alpha-olefin, preferably and C₂ to C₂₀ alpha-olefin, more preferably anyC₂ to C₁₂ alpha-olefin, more preferably ethylene, propylene, and butene,most preferably ethylene. Dienes may be used in the processes describedherein, preferably alpha, omega-dienes are used alone or in combinationwith mono-alpha olefins.

Preferred oligomerization processes may be run in the presence ofvarious liquids, particularly aprotic organic liquids. Preferably thehomogeneous catalyst system, ethylene, alpha-olefins, and product aresoluble in these liquids. A supported (heterogeneous) catalyst systemmay also be used. Suitable liquids for both homo- and heterogeneouscatalyst systems, include alkanes, alkenes, cycloalkanes, selectedhalogenated hydrocarbons, aromatic hydrocarbons, and in some cases,hydrofluorocarbons. Useful solvents specifically include hexane,toluene, cyclohexane, and benzene.

The instant invention may also be used to obtain mixtures ofalpha-olefins containing desirable numbers of carbon atoms. Factor Kfrom the Schulz-Flory theory (see for instance B. Elvers, et al., Ed.Ullmann's Encyclopedia of Industrial Chemistry, Vol. A13, VCHVerlagsgesellschaft mbH, Weinheim, 1989, p. 243-247 and 275-276) servesas a measure of these α-olefins' molecular weights. From this theory,K=n(Cn+2 olefin)/n(Cn olefin), where n(Cn olefin) is the number of molesof olefin containing n carbon atoms, and n(Cn+2 olefin) is the number ofmoles of olefin containing n+2 carbon atoms, or in other words the nexthigher oligomer of Cn olefin. From this can be determined the weight(mass) fractions of the various olefins in the resulting product. Theability to vary this factor provides the ability to choose thethen-desired olefins.

Invention-made alpha-olefins may be further polymerized with otherolefins to form more oligomers or even form homopolymers and copolymersof the alpha olefins produced. These polymers may be made by a number ofknown methods, such as Ziegler-Natta-type polymerization, metallocenecatalyzed polymerization, and other methods. See for instance WO96/23010, and Angew. Chem., Int. Ed. Engl., vol. 34, p. 1143-1170(1995); European Patent Application, 416,815; and U.S. Pat. No.5,198,401, for information about metallocene-type catalysts, and J. BoorJr., Ziegler-Natta Catalysts and Polymerizations, Academic Press, NewYork, 1979 and G. Allen, et al., Ed., Comprehensive Polymer Science,Vol. 4, Pergamon Press, Oxford, 1989, pp. 1-108, 409-412 and 533-584.For information about Ziegler-Natta-type catalysts, see H. Mark, et al.,Ed., Encyclopedia of Polymer Science and Engineering, Vol. 6, John Wiley& Sons, New York, 1992, p. 383-522.

Preferred oligomerization processes include oligomerizing ethylene toC4-C26 linear alpha-olefins.

Oligomers produced herein may be used as polyolefin feed stocks. Theymay be used as a mixture of olefins alone, as a mixture of olefins addedto other olefins, or they may be separated into fractions, and then usedalone or in combination with other olefins to form polyolefins.Additionally, alpha-olefins produced herein may be converted to alcoholsby known processes, these alcohols being useful for a variety ofapplications such as intermediates for detergents or plasticizers.Typical processes for the conversion of alpha-olefins to alcoholsinclude, but are not limited to, the oxo process followed byhydrogenation, or by a modified, single-step oxo process, see forinstance B. Elvers, et al., Ed., Ullmann's Encyclopedia of ChemicalTechnology, 5th Ed., Vol. A18, VCH Verlagsgesellschaft mbH, Weinheim,1991, p. 321-327.

EXAMPLES Preparation of Ligands

The electrospray (ES) mass spectra were recorded using a micromassQuattra LC mass spectrometer with methanol as the matrix [Masslynxsoftware; open-access autosampler injection]. The infrared spectra wererecorded as Nujol mulls between 0.5 mm NaCl plates on a Perkin Elmer1600 series. 1H and 13C NMR spectra were recorded on a Bruker ARXspectrometer 250/300 Hz; chemical shifts (ppm) are referred to theresidual protic solvent peaks. The reagents, sodium t-butoxide the arylbromides were purchased from Aldrich Chemical Co. and used withoutfurther purification. rac-BINAP(rac-2,2′-bi(diphenylphosphino)-1,1′-binaphthyl) was purchased fromStrem Chemical Co. The compounds, Pd₂(dba)₃(tris(dibenzylideneaeacetone)dipalladium(0) used as the chloroformsolvate) [1], {(2-C₅H₄N)CH₂}2NH (dpa) [2], (H₂NCH₂CH₂){2-C₅H₄N)CH₂}NH[3], 2-Bromo-1,3,5-i-Pr₃C₆H_(2 [)4], and N-tosylaziridine [5] wereprepared according to a previously reported procedures referenced below.Pd₂(dba)₃ can also be purchased from Strem Chemical Co. All otherchemicals were obtained commercially and used without furtherpurification.

[1] T. Ukai, H. Kawazura, Y. Ishii, J. Bonnet and J. A. Ibers, J.Organomet. Chem., 1974, 65, 253; [2] H. J. Hoorn, P. de. Joode, W. L.Driessen and J. Reedijk, Recueil des Travaux. Chim. Des. Pays-Bas.,1996, 115, 191; [3] Y. Maeda, K. Kawano and T. Oniki, J. Chem. Soc.,Dalton Trans., 1995, 3533; [4] G. M. Whitesides, M. Eisenhut and W. M.Bunting, J. Amer. Chem. Soc., 1974, 96, 5398; [5] B. Dietrich, M. W.Hossein, J.-M. Lehn and R. B. Sessions, Helv. Chim. Acta, 1985, 68, 289.

Examples 1-3, 5-7

Example 1 Preparation of(N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine (1a)

A Schlenk tube was charged with (H₂NCH₂CH_(2{)2-C₅H₄N)CH₂}NH (1.00 g,6.62 mmol), 2-bromo-m-xylene (0.88 cm3, 1.23 g, 6.62 mmol), Pd2(dba)3(0.030 g, 0.033 mmol, 0.005 equiv.), rac-BINAP (0.062 g, 0.099 mmol,0.015 equiv.), NaOBut (1.91 g, 19.9 mmol, 3 equiv.) and toluene (40cm3). The reaction mixture was heated to 100 oC and stirred for a periodof 4 days. After cooling to room temperature, the solvent was removedunder reduced pressure to afford an oily residue. The residue wasdissolved in diethyl ether (30 cm3) and washed with water (3×30 cm3) andsaturated sodium chloride solution (3×30 cm3). The organic layer wasseparated and dried over magnesium sulfate. The volatiles were removedunder reduced pressure and the residue left under vacuum at 70° C. 24 hto give 1.33 g (79%) of 1a as a viscous oil.

Compound 1a: ES mass spectrum, m/z 256 [M+H]+. IR (nujol mull, cm-1), ν3350 (N—H, medium). 1H NMR (CDCl₁₃, 250 MHz, ppm), δ 2.20 (s, 6H, Meo),2.77 (t, 2H, 3JH-H 5.7 Hz, CH₂), 3.02 (t, 2H, 3JH-H 5.7 Hz, CH₂, 3.85(s, 2H, Py-CH₂), 6.70 (m, 1H, Ar—CH), 6.88 (m, 2H, Ar—CH), 7.06 (m, 1H,Py-CH), 7.20 (d, 1H, 3JH-H 7.8 Hz, Py-CH), 7.52 (dt, 1H, 3JH-H 7.8 Hz,Py-CH), 8.50 (dd, 1H, 3JH-H 4.4 Hz, Py-CH). 13C NMR (CDCl₃, 250 MHz,ppm, 1H composite pulse decoupled): δ 19.0 (2C, Meo), 48.4 (1C, CH₂),50.0 (1C, CH₂), 55.4 (1C, Py-CH₂), 121.9 (1C, Py-CH), 122.4 (1C, Py-CH),122.6 (1C, Ar—CH), 129.2 (2C, Ar—CH), 129.7 (2C, Ar—C), 136.9 (1C,Py-CH), 146.8 (1C, Ar—C), 149.7 (1C, Py-CH), 160.3 (1C, Py-C).

Example 2 Preparation of(N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine (1b)

Compound 1b was prepared using a similar route and the same molarquantities of reagents as that outlined for 1a (Example 1) employing2-bromomesitylene (1.00 cm3, 1.32 g, 6.62 mmol) as the aryl bromide.Compound 1b was obtained analytically pure in good yield (1.34 g, 75%)as a red oil.

Compound 1b: ES mass spectrum, m/z 270 [M+H]+. NMR (CDCl₃, 293 K): 1HNMR δ 8.7-7.1 (m, 4H, Py-H), 6.84 (s, 2H, Ar—H), 3.98 (s, 2H, Py-CH₂,2H), 3.09 (t, 2H, CH₂), 2.89 (t, 2H, CH₂), 2.29 (s, 6H, Meo) and 2.21(s, 3H, Mep). 13C (1H composite pulse decoupled), δ 159.9 (s, C, Py),149.4 (s, C, Py), 143.8 (s, C, Ar), 136.5 (s, C, Py), 129.5 (s, C, Ar),129.1 (s, C, Ar), 122.2 (s, C, Py), 122.1 (s, C, Py), 122.0 (s, C, Ar),55.1 (s, CH₂), 49.7 (s, CH₂), 48.4 (s, CH₂), 20.6 (s, Mep) and 18.5 (s,Meo).

Example 3 Preparation of(N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine (1c)

Compound 1c was prepared using a similar route and the same molarquantities of reagents as that outlined for 1a (Example 1) employing2-bromo-1,3,5-triisopropylbenzene (1.87 g, 6.62 mmol) as the arylbromide. Compound 1c was obtained analytically pure in reasonable yield(1.17 g, 50%) as a red oil.

Compound 1c: ES mass spectrum, m/z 353 [M+H]+.

Example 4 Preparation of bis(2-picolyl)(2-aminoethyl)amine (dpea)

The compound was prepared via a two-step procedure:

(i) To a three-necked round bottom flask equipped with a refluxcondenser, dropping funnel and a magnetic stirrer was added{(2-C₅H₄N)CH₂}₂NH (19.900 g, 100 mmol) dissolved in acetonitrile (250cm³). The yellow solution was brought to reflux and N-tosylaziridine inacetonitrile (200 cm³) was added dropwise over 1 h, to give a dark redsolution, which was heated to reflux for an additional 5 h. The dark redsolution was concentrated on a rotary evaporator and dried under reducedpressure overnight to give 39.204 g (99%) of(TsNHCH₂CH₂){(2-C₅H₄N)CH₂}₂N as a dark red oil.Compound (TsNHCH₂CH₂){(2-C₅H₄N)CH₂}₂N: ES mass spectrum, m/z 419,[M+Na]⁺, 397 [M+H]⁺. ¹H NMR (CDCl₃, 250 MHz, ppm): δ 2.36 (s, 3H, CH₃),2.77 (t, 2H, ³J_(H-H) 5.25 Hz, CH₂), 3.03 (q, 2H, ³J_(H-H) 5.25 Hz,CH₂), 3.76 (s, 4H, CH₂), 7.16 (m, 6H, CH), 7.57 (m, 2H, ³J_(H-H) 6 Hz,CH), 7.71 (d, 2H, ³J_(H-H) 8 Hz, CH), 8.58 (d, 2H, ³J_(H-H) 4.6 Hz, CH).(ii) To (N-tosyl-2-aminoethyl)bis(2-pyridylmethyl)amine (39.204 g, 99.0mmol) in a round bottom flask equipped with reflux condenser was addedconcentrated H₂SO₄ (300 cm³). The dark red solution was heated at 130°C. After 3 days the reaction mixture was cooled in an ice bath. Thedropwise addition of diethyl ether (4000 cm³) and absolute ethanol (3000cm³) gave a dark brown precipitate. The brown precipitate was filteredand immediately dissolved in saturated NaOH. The organic layer wasextracted by washing with chloroform, the resulting red organic phasedried over MgSO₄ and concentrated on a rotary evaporator, to give 17.449g (73%) of (H₂NCH₂CH₂){(2-C₅H₄N)CH₂}₂N as a red oil.

Compound (H₂NCH₂CH₂){2-C₅H₄N)CH₂}2N: ES mass spectrum, m/z 243, [M+H]+.IR (CH₂Cl₂, cm-1): ν 3360 (N—H), 3288 (N—H, C—H). 1H NMR (CDCl₃, 250MHz, ppm): δ 1.65 (s, 2H, NH₂), 2.67 (t, 2H, 3JH-H 5.7 Hz, CH₂), 2.80(t, 2H, 3JH-H 5.6 Hz, CH₂), 3.85 (s, 4H, Py-CH₂), 7.14 (dt, 2H, 3JH-H7.5, 5 Hz, 4JH-H 1.4 Hz, Py-CH), 7.49 (d, 2H, 3JH-H 7.75 Hz, Py-CH),7.65 (dt, 2H, 3JH-H 7.5 Hz, 4JH-H 1.6 Hz, Py-CH), 8.53 (d, 2H, 3JH-H 5Hz, 4JH-H 1.6 Hz, Py-CH). 13C NMR (CDCl₃, 300 MHz, ppm, 1H compositepulse decoupled): δ 39.9 (1C, CH₂), 57.8 (1C, CH₂), 61.1 (2C, Py-CH₂),122.4 (2C, Py-CH), 123.4 (2C, Py-CH), 136.8 (2C, Py-CH), 149.4 (2C,Py-CH), 160.0 (2C, Py-C).

Example 5 Preparation ofbis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine (2a)

A Schlenk tube was charged with (H₂NCH₂CH₂){2-C₅H₄N)CH₂}2N (1.60 g, 6.62mmol), 2-bromo-m-xylene (0.88 cm3, 1.23 g, 6.62 mmol), Pd2(dba)₃ (0.030g, 0.033 mmol, 0.005 equiv.), rac-BINAP (0.062 g, 0.099 mmol, 0.015equiv.), NaOBut (1.91 g, 19.9 mmol, 3 equiv.) and toluene (40 cm3). Thereaction mixture was heated to 100° C. and stirred for a period of 4days. After cooling to room temperature, the solvent was removed underreduced pressure to afford an oily residue. The residue was dissolved indiethyl ether (30 cm3) and washed with water (3×30 cm3) and saturatedsodium chloride solution (3×30 cm3). The organic layer was separated anddried over magnesium sulfate. The volatiles were removed under reducedpressure and the residue left under vacuum at 70° C. for 24 h to give1.71 g (75%) of 2a as a viscous red oil.

Compound 2a: ES mass spectrum: m/z 369 [M+Na]+, 347 [M+H]+. IR (nujolmull, cm-1): ν 3354 (C—N), 1589 (pyridine C═N, C═C), 1H NMR(CDCl_(3—)250 MHz, ppm): δ 2.2 (s, 6H, —CH₃), 2.8 (t, 2H, 3JH-H 6 Hz,CH₂), 3.1 (t, 2H, 3JH-H 6 Hz, CH₂), 3.8 (s, 4H, CH₂), 6.68 (m, 1H, 3JH-H7.56, 7.12 Hz, CH), 6.87 (t, 1H, 3JH-H 7.37 Hz, CH), 7.07 (m, 2H, 3JH-H4.8, 6 Hz, CH), 7.42 (d, 2H, 3JH-H 8.1 Hz, C₄H), 7.6 (t, 2H, 3JH-H 6,7.8 Hz, CH), 8.47 (d, 2H, 3JH-H 4.8 Hz, CH). 13C NMR (CDCl₃, 250 MHz,ppm): δ 19.2 (2C, CH₃), 46.2 (1C, CH₂), 55.0 (1C, CH₂), 60.8 (2C, CH₂),121.5 (1C, CH), 122.5 (2C, CH), 123.5 (2C, CH), 129.2 (2C, CH), 136.8(2C, CH), 128.9 (2C, C), 147.0 (1C, C), 149.6 (2C, CH), 159.7 (2C, C).

Example 6 Preparation ofbis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine (2b)

Compound 2b was prepared using a similar route and the same molarquantities of reagents as that outlined for 2a (Example 5) employing2-bromomesitylene (1.00 cm3, 1.32 g, 6.62 mmol) as the aryl bromide.Compound 2b was obtained as a red oil in moderate yield (0.99 g, 42%).

Compound 2b: ES mass spectrum: m/z 383 [M+Na]+, 361 [M+H]+. IR (nujolmull, cm-1) ν 3355 (C—N), 1589 (pyridine C═N, C═C). 1H NMR (CDCl₃, 250MHz, ppm): δ 2.12 (s, 9H, CH₃), 2.76 (t, 2H, 3JH-H 6 Hz, CH₂), 3.02 (t,2H, 3JH-H 6 Hz, CH₂), 3.81 (s, 4H, CH₂), 6.69 (s, 2H, CH), 7.06 (t, 2H,3JH-H 7.5, 5 Hz, CH), 7.42 (d, 2H, 3JH-H 8 Hz, CH), 7.56 (m, 2H, 3JH-H7.5 Hz, CH), 8.46 (d, 2H, 3JH-H 5 Hz, CH). ¹³C NMR (CDCl₃, 250 MHz,ppm): δ 17.6 (2C, CH₃), 19.5 (1C, CH₃), 45.1 (1C, CH₂), 53.6 (1C, CH₂),59.3 (2C, CH₂), 121.0 (2C, CH), 122.1 (2C, CH), 127.9 (2C, C), 128.4(2C, CH), 129.5 (1C, C), 135.3 (2C, CH), 142.9 (1C, C), 148.1 (2C, CH),158.3 (2C, C).

Example 7 Preparation ofbis(2-picolyl)(N-2,4-dimethylphenyl-2-aminoethyl)amine (2c)

Compound 2c was prepared using a similar route and the same molarquantities of reagents as that outlined for 2a (Example 5) employing5-bromo-m-xylene (0.88 cm3, 1.23 g, 6.62 mmol) as the aryl bromide.Compound 2c was obtained as a red oil in good yield (1.56 g, 68%).

Compound 2c: ES mass spectrum: m/z 369 [M+Na]+, 347 [M+H]+. IR (nujolmull, cm-1): ν 3350 (C—N), 1588 (pyridine C═N, C═C). 1H NMR (CDCl₃, 250MHz, ppm): δ 2.10 (s, 3H, CH₃), 2.13 (s, 3H, CH₃), 2.83 (t, 2H, 3JH-H 6Hz, CH₂), 3.12 (t, 2H, 3JH-H 6 Hz), 3.79 (s, 4H), 6.35 (d, 1H, 3JH-H8.47 Hz, CH), 6.79 (m, 2H, 3JH-H 6 Hz, CH), 7.05 (t, 2H, 3JH-H 7, 6, 5Hz, CH), 7.37 (d, 2H, 3JH-H 7.8 Hz, CH), 7.53 (t, 2H, 3JH-H 7.5 Hz, CH),8.45 (d, 2H, 3JH-H 4.8 Hz, CH). ¹³C NMR (CDCl₃, 250 MHz, ppm): δ 17.9(1C, CH₃), 20.73 (1C, CH₃), 41.7 (1C), 53.1 (1C, CH₂), 60.6 (2C, CH₂),110.3 (1C, CH), 122.5 (2C, CH), 122.5 (2C, C), 123.4 (2C, CH), 126.1(1C, C), 127.7 (1C, CH), 131.2 (1C, CH), 136.8 (2C, CH), 144.7 (1C, C),149.6 (2C, CH), 159.8 (2C, C).

Preparation of Complexes

All complexation reactions were carried out under an atmosphere of dry,oxygen-free nitrogen, using standard Schlenk tube techniques or in anitrogen purged glove box. n-Butanol was dried and deoxygenated bydistillation over sodium metal under nitrogen. The metal dichlorideswere purchased from Aldrich Chemical Co. and used without any furtherpurification. FAB mass spectra were recorded using a Kratos Conceptspectrometer with NBA (nitrobenzyl alcohol) as the matrix [samplesplaced on the end of probe within matrix and bombarded with xenon atomsat ca. 7 kV; Mach3 software, probe temperature 50° C.]. Elementalanalyses were performed by S. Boyer at the Department of Chemistry,University of North London (UK). Data for the crystal structuredeterminations were collected on a Bruker APEX 2000 CCD diffractometerand solved using SHELXTL version 6.10. Magnetic susceptibility studieswere performed using an Evans Balance at ambient temperature.

Examples 8-20

Example 8 Synthesis of[(N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobalt dichloride(3a)

A solution of 1a (0.100 g, 0.39 mmol) in n-butanol (5 cm3) wasintroduced dropwise to a solution of CoCl₂ (0.051 g, 0.39 mmol) inn-butanol (5 cm3) at 90° C. to form a green/blue solution. After beingstirred at 90° C. for 1 h, the reaction was allowed to cool to roomtemperature. The reaction mixture was concentrated and hexane added toinduce precipitation of the product. The suspension was stirredovernight, filtered, washed with hexane (2×30 cm3) and dried underreduced pressure to afford 0.121 g (80%) of 3a as a pale green solid.

Complex 3a: FAB mass spectrum: m/z 385 [M]+, 350 [M−Cl]+ μ_(eff) (EvansBalance) 3.8 BM. C1₆H₂₁N₃CoCl₂: calcd. C, 49.89; H, 5.49; N, 10.91;found C, 50.01; H, 5.61; N, 10.80%.

Layering of an acetonitrile solution of 3a with hexane gave bluecrystals suitable for a single crystal X-ray diffraction study (FIG. 1).

Example 9 Synthesis of[(N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]cobaltdichloride (3b)

Using the same procedure and molar quantities of reagents as thatoutlined for 3a (Example 8) with 1b (0.105 g, 0.39 mmol) as the ligand,complex 3b was obtained as a pale green powder in good yield (0.118 g,75%).

Complex 3b: FAB mass spectrum: m/z 399 [M]+, 364 [M−Cl]+ μ_(eff) (EvansBalance) 3.7 BM. C1₇H₂₃N₃CoCl₂.CH₃CN calcd. C, 51.83; H, 5.95; N, 12.73;found C, 51.84; H, 5.97; N, 12.61%.

Layering of an acetonitrile solution of 3b with hexane gave bluecrystals suitable for a single crystal X-ray diffraction study (FIG. 2).

Example 10 Synthesis of[(N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]cobaltDichloride (3c)

Using the same procedure and molar quantities of reagents as thatoutlined for 3a (Example 8) with 1c (0.137 g, 0.39 mmol) as the ligand,complex 3c was obtained as a pale green powder in good yield (0.140 g,75%).

Complex 3c: FAB mass spectrum: m/z 483 [M]+, 448 [M−Cl]+. μ_(eff) (EvansBalance) 3.9 BM.

Example 11 Synthesis of[(N-2,6-dimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron dichloride(4a)

A solution of 1a (0.100 g, 0.39 mmol) in n-butanol (5 cm3) wasintroduced dropwise to a solution of FeCl2 (0.049 g, 0.39 mmol) inn-butanol (5 cm3) at 90 oC to form a green solution. After being stirredat 90 oC for 1 h, the reaction was allowed to cool to room temperature.The reaction mixture was concentrated and hexane added to induceprecipitation of the product. The suspension was stirred overnight,filtered, washed with hexane (2×30 cm3) and dried under reduced pressureto afford 0.115 g (77%) of 4a as a yellow-green solid.

Complex 4a: FAB mass spectrum: m/z 382 [M]+, 347 [M−Cl]+ μ_(eff) (EvansBalance) 4.9 BM. C1₆H₂₁N₃FeCl₂: calcd. C, 50.29; H, 5.54; N, 11.00;found C, 49.65; H, 5.62; N, 10.62%.

Layering of an acetonitrile solution of 4a with hexane gave yellowcrystals suitable for a single crystal X-ray diffraction study (FIG. 3).

Example 12 Synthesis of[(N-2,4,6-trimethylphenyl-2-aminoethyl)(2-picolyl)amine]iron Dichloride(4b)

Using the same procedure and molar quantities of reagents as thatoutlined for 4a (Example 11) with 1b (0.105 g, 0.39 mmol) as the ligand,complex 4b was obtained as a yellow-brown powder in good yield (0.110 g,71%). Recrystallization of 4b could be achieved by the slow cooling of ahot acetonitrile solution of 4b.

Complex 4b: FAB mass spectrum: m/z 396 [M]+, 361 [M−Cl]+ μ_(eff) (EvansBalance) 5.0 BM. C₁₇H₂₂N₃FeCl₂: calcd. C, 51.68; H, 5.61; N, 10.63;found C, 51.59; H, 5.51; N, 10.63%.

Example 13 Synthesis of[(N-2,4,6-triisopropylphenyl-2-aminoethyl)(2-picolyl)amine]ironDichloride (4c)

Using the same procedure and molar quantities of reagents as thatoutlined for 4a (Example 11) with 1c (0.137 g, 0.39 mmol) as the ligand,complex 4c was obtained as a yellow-brown powder in good yield (0.102 g,55%). Recrystallization of 4c could be achieved by the slow cooling of ahot acetonitrile solution of 4c.

Complex 4c: FAB mass spectrum: m/z 480 [M]+, 445 [M−Cl]+. μ_(eff) (EvansBalance) 5.1 BM.

Example 14 Synthesis of [{bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine}cobalt Dichloride]₂ (5a)

A solution of 2a (0.100 g, 0.29 mmol) in n-butanol (5 cm3) was addeddropwise to a solution of CoCl₂ (0.037 g, 0.32 mmol) in n-butanol (5cm3) at 90° C. to yield a green solution. After being stirred at 90° C.for 1 h, the reaction was allowed to cool to room temperature. Thereaction mixture was concentrated and hexane added to induceprecipitation of the product. The suspension was stirred overnight,filtered, washed with hexane (2×30 cm3) and dried under reduced pressureto afford 5a as a pale green solid (0.110 g, 80%).

Complex 5a: FAB mass spectrum: m/z 917 [M−Cl]+, 441 [M/2−Cl]+.

Example 15 Preparation of[{bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine}cobaltDichloride]₂ (5b)

Using the same procedure and molar quantities of reagents as thatoutlined for 5a (Example 14) with 2b (0.104 g, 0.29 mmol) as the ligand,complex 5b was obtained as a green solid in good yield (0.094 g, 67%).

Complex 5b: FAB mass spectrum: m/z 945 [M−Cl]+, 455 [M/2−Cl]+. μ_(eff)(Evans Balance) 3.8 BM (per Co center).

Example 16 Preparation of[bis(2-picolyl)(N-2,4-dimethylphenyl-2-aminoethyl)amine]cobaltDichloride (5c)

Using the same procedure and molar quantities of reagents as thatoutlined for 5a (Example 14) with 2c (0.100 g, 0.29 mmol) as the ligand,complex 5c was obtained as a green solid in good yield (0.102 g, 67%).

Complex 5c: FAB mass spectrum: m/z 475 [M]+, 440 [M−Cl]+. μ_(eff) (EvansBalance) 4.2 BM.

Example 17 Synthesis of[{bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine}ironDichloride]₂ (6a)

A solution of 2a (0.100 g, 0.29 mmol) in n-butanol (5 cm³) was addeddropwise to a solution of FeCl₂ (0.037 g, 0.29 mmol) in n-butanol (5cm³) at 90° C. to yield a green solution. After being stirred at 90° C.for 1 h, the reaction was allowed to cool to room temperature. Thereaction mixture was concentrated and hexane added to induceprecipitation of the product. The suspension was stirred overnight,filtered, washed with hexane (2×30 cm³) and dried under reduced pressureto afford 6a as a yellow green solid (0.102 g, 75%).

Complex 6a: FAB mass spectrum: m/z 910 [M−Cl]⁺, 437 [M/2−Cl]⁺.

Example 18 Preparation of[{bis(2-picolyl)(N-2,4,6-trimethylphenyl-2-aminoethyl)amine}ironDichloride]₂ (6b)

Using the same procedure and molar quantities of reagents as thatoutlined for 6a (Example 17) with 2b (0.104 g, 0.29 mmol) as the ligand,complex 6b was obtained as a yellow green solid in good yield (0.094 g,67%).

Complex 6b: FAB mass spectrum: m/z 939 [M−Cl]⁺, 487 [M/2]⁺, 452[M/2−Cl]⁺.

Example 19 Preparation of[bis(2-picolyl)(N-2,4-dimethylphenyl-2-aminoethyl)amine]iron Dichloride(6c)

Using the same procedure and molar quantities of reagents as thatoutlined for 6a (Example 17) with 2c (0.100 g, 0.29 mmol) as the ligand,complex 6c was obtained as a yellow green solid in good yield (0.079 g,58%).

Complex 6c: FAB mass spectrum: m/z 473 [M]⁺, 438 [M−Cl]⁺. C₂₂H₂₆N₄FeCl₂:calcd. C, 55.84; H, 5.54; N, 11.84; found C, 55.79; H, 5.59; N, 11.84%.

Layering of an acetonitrile solution of 6c with hexane gave yellowcrystals suitable for a single X-ray diffraction study (FIG. 4).

Example 20 Preparation of[{bis(2-picolyl)(N-2,6-dimethylphenyl-2-aminoethyl)amine}manganeseDichloride]₂ (7a)

A solution of 2a (0.100 g, 0.29 mmol) in n-butanol (5 cm³) was addeddropwise to a solution of MnCl₂ (0.049 g, 0.29 mmol) in n-butanol (5cm³) at 90° C. to yield a green solution. After being stirred at 90° C.for 1 h, the reaction was allowed to cool to room temperature. Thereaction mixture was concentrated and hexane added to induceprecipitation of the product. The suspension was stirred overnight,filtered, washed with hexane (2×30 cm³) and dried under reduced pressureto afford 7a as a pale pink solid (0.099 g, 70%).

Complex 7a: FAB mass spectrum: m/z 908 [M−Cl]⁺, 436 [M/2−Cl]⁺.

Layering of an acetonitrile solution of 7a with hexane gave clearcrystals on prolonged standing (FIG. 5).

Oligomerizations

The reagents used in the oligomerization tests were Ethylene Grade 3.5(supplied from BOC) and methylalumoxane (MAO, 10% wt solution intoluene, supplied by Aldrich). GC measurements were obtained usingeither a Perkin Elmer Autosystem XL chromatogram (University ofLeicester) [Column type ZB-5; Column length 30 m; Column diameter 0.25mm; Initial column temperature 50-100° C.] with a Mass Spectrometerdetector [Perkin Elmer Tubo; Ionization mode, electron impact; Massrange 50-500 amu; Solvent CH₂Cl₂] or using an HP 5890 chromatogram(ExxonMobil) [Column type SGE HT-5; Column length 12 m; Column diameter0.53 mm; Initial column temperature 55° C.] with a flame ionizationdetector (FID).

Example 21—Schlenk Tube Oligomerization

The complexes 3 and 4 made in Examples 8-12 above were dissolved orsuspended in toluene (40 cm³) and MAO introduced. The tube was purgedwith ethylene and the contents stirred under one bar of ethylenepressure at 25° C. for the duration of the oligomerization. After halfan hour the oligomerization was terminated by the addition of aqueousHCl. The aqueous phase was separated and washed with toluene (2×25 ml)and all organic layers combined and dried over anhydrous magnesiumsulfate. The solutions were prepared for quantitative GC analysis bydiluting the organic phases to 100 ml with toluene in a volumetric flaskand adding 1-heptadecene (50 μl) as an internal standard. The runs aresummarized in Table 2. FIG. 6 shows the Schulz-Flory distribution forruns 3 and 4 using pre-catalysts, 3c and 4c, respectively. FIG. 7 showsthe oligomer distribution of oligomer fractions versus carbon number forruns 3 and 4 using pre-catalysts 3c and 4c, respectively.

TABLE 2 Ethylene oligomerization results from precatalysts 3 and 4.^(a)Pre- Oligo- Activity catalyst Activator^(b) mers (g/mmol/ K Run (mmol)(mmol/equiv.) (g)^(c) h/bar)

^(d) β^(e) 1 3a (0.010) MAO (4/400) 0.295 59 0.76 0.32 2 3b (0.010) MAO(4/400) 0.131 26 0.76 0.32 3 3c (0.010) MAO (4/400) 0.381 76 0.80 0.25 44c (0.010) MAO (4/400) 0.0295 6 0.80 0.25 5 4c (0.010) MAO (10/1000)0.0260 5 0.74 0.35 ^(a)General Conditions: Toluene solvent (40 cm³), 25°C., reaction time 30 min, ethylene pressure 1 bar, reaction quenchedwith dilute HCl; ^(b)MAO = methylalumoxane; ^(c)Determined from GC usingextrapolated values based on a Schulz-Flory distribution for C₄-C₈ andC₂₂-C₂₆ for runs 1-3 and C₄-C₁₀ for C₂₆ for runs 4/5 employing1-heptadecene as an internal standard. ^(d)K =

= n(C_(n+2) olefin)/n(C_(n) olefin), where n(C_(n) olefin) is the numberof moles of olefin containing n carbon atoms, and n(C_(n+2) olefin) isthe number of moles of olefin containing n + 2 carbon atoms, and is therate of propagation over the sum of the rate of propagation and the rateof chain transfer. ^(e)β = (1 −

)/

and is the rate of chain transfer over the rate of propagation.

All documents described herein are incorporated by reference herein,including any priority documents and testing procedures for alljurisdictions in which such incorporation is permitted. As is apparentfrom the foregoing general description and the specific embodiments,while forms of the invention have been illustrated and described,various modifications can be made without departing from the spirit andscope of the invention. Accordingly, it is not intended that theinvention be limited thereby. Certain features of the present inventionare described in terms of a set of numerical upper limits and a set ofnumerical lower limits. This specification discloses all ranges formedby any combination of these limits. All combinations of these limits arewithin the scope of the invention unless otherwise indicated.

1. A catalyst precursor represented by the formula:

wherein: M is a group 7, 8, 9, or 10 transition metal; N is nitrogen; Cis carbon; X is, independently, an anionic monodentate ligand, or both Xgroups together form a bidentate dianionic ligand; R′ is, independently,a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, asubstituted halocarbyl, a cyclic ring comprising two R′ groups on thesame carbon, a polycyclic ring comprising two R′ groups on the samecarbon, a cyclic ring comprising two or more R′ groups on adjacentcarbons, or a polycyclic ring comprising two or more R′ groups onadjacent carbons; x is 1, 2, 3 or 4; y is 1, 2, 3 or 4; R¹, R², R³ or R⁴is, independently, a hydrogen, a hydrocarbyl, a substituted ahydrocarbyl, a halocarbyl, a substituted halocarbyl, a cyclic ringstructure comprising two adjacent R¹, R², R³ or R⁴, or a polycyclic ringstructure comprising two adjacent R¹, R², R³ or R⁴; R⁵ is a hydrogen,hydrocarbyl or halocarbyl; and R⁶ is a C₃ to C₅₀ hydrocarbyl or a C₃ toC₅₀ halocarbyl, and wherein the central nitrogen atom is a non-pyridinalnitrogen atom and is not bonded to its adjacent atoms by a multibond. 2.A catalyst precursor represented by the formula:

wherein: each M is, independently, a group 7, 8, 9, 10, or 11 transitionmetal; N is nitrogen; C is carbon; each X is, independently, an anionicmonodentate ligand, or two X groups together may form a bidentatedianionic ligand; R′ is, independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, acyclic ring comprising two R′ groups on the same carbon, a polycyclicring comprising two R′ groups on the same carbon, a cyclic ringcomprising two or more R′ groups on adjacent carbons, or a polycyclicring comprising two or more R′ groups on adjacent carbons; x is,independently, 1, 2, 3 or 4; y is, independently, 1, 2, 3 or 4; R¹, R²,R³ or R⁴ is, independently, a hydrogen, a hydrocarbyl, a substituted ahydrocarbyl, a halocarbyl, a substituted halocarbyl, a cyclic ringstructure comprising two adjacent R¹, R², R³ or R⁴, or a polycyclic ringstructure comprising two adjacent R¹, R², R³ or R⁴; R⁵ is,independently, a hydrogen, hydrocarbyl or halocarbyl; R⁶ is,independently, a C₃ to C₅₀ hydrocarbyl or a C₃ to C₅₀ halocarbyl; and R⁷is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, asubstituted halocarbyl; a substituted hydrocarbyl comprising aheteroatom, wherein the heteroatom is bonded to M, or a substitutedhalocarbyl comprising a heteroatom, wherein the heteroatom is bonded toM.
 3. A catalyst precursor represented by the formula:

wherein: each M is, independently, a group 7, 8, 9, 10, or 11 transitionmetal; N is nitrogen; C is carbon; each X is, independently, an anionicmonodentate ligand, or two X groups together may form a bidentatedianionic ligand; R′ is, independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, acyclic ring comprising two R′ groups on the same carbon, a polycyclicring comprising two R′ groups on the same carbon, a cyclic ringcomprising two or more R′ groups on adjacent carbons, or a polycyclicring comprising two or more R′ groups on adjacent carbons; x is 1, 2, 3or 4; y is 1, 2, 3 or 4; R¹, R², R³ or R⁴ is, independently, a hydrogen,a hydrocarbyl, a substituted a hydrocarbyl, a halocarbyl, a substitutedhalocarbyl, a cyclic ring structure comprising two adjacent R′, R², R³or R⁴, or a polycyclic ring structure comprising two adjacent R′, R², R³or R⁴; R⁵ is a hydrogen, hydrocarbyl or halocarbyl; and R⁶ is a C₃ toC₅₀ hydrocarbyl or a C₃ to C₅₀ halocarbyl.
 4. A catalyst precursorrepresented by the formula:

wherein: M is a group 7, 8, 9, or 10 transition metal; N is nitrogen;each X is, independently, an anionic monodentate ligand, or both Xgroups together may form a bidentate dianionic ligand; each R¹ is,independently, a hydrogen, a hydrocarbyl, a substituted a hydrocarbyl, ahalocarbyl, or a substituted halocarbyl; R⁵ is a hydrogen, hydrocarbylor halocarbyl; and R⁶ is a C₃ to C₅₀ hydrocarbyl or a C₃ to C₅₀halocarbyl, and wherein the central nitrogen atom is a non-pyridinalnitrogen atom and is not bonded to its adjacent atoms by a multibond. 5.A catalyst precursor represented by the formula:

wherein: M is, independently, a group 7, 8, 9, 10, or 11 transitionmetal; N is nitrogen; X is, independently, an anionic monodentateligand, or two X groups together may form a bidentate dianionic ligand;R¹ is a hydrogen, a hydrocarbyl, a substituted a hydrocarbyl, ahalocarbyl, or a substituted halocarbyl; R⁵ is, independently, ahydrogen, hydrocarbyl or halocarbyl; R⁶ is, independently, a C₃ to C₅₀hydrocarbyl or a C₃ to C₅₀ halocarbyl; and R⁷ is a hydrogen, ahydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substitutedhalocarbyl; a substituted hydrocarbyl comprising a heteroatom, whereinthe heteroatom is bonded to M, or a substituted halocarbyl comprising aheteroatom, wherein the heteroatom is bonded to M.
 6. A catalystprecursor represented by the formula:

wherein: M is, independently, a group 7, 8, 9, 10, or 11 transitionmetal; N is nitrogen; X is, independently, an anionic monodentateligand, or two X groups together may form a bidentate dianionic ligand;R¹ is a hydrogen, a hydrocarbyl, a substituted a hydrocarbyl, ahalocarbyl, or a substituted halocarbyl; R⁵ is, independently, ahydrogen, a hydrocarbyl or a halocarbyl; R⁶ is, independently, a C₃ toC₅₀ hydrocarbyl or a C₃ to C₅₀ halocarbyl.
 7. The catalyst precursor ofclaim 1, wherein M comprises one or more of cobalt, iron or manganese.8. The catalyst precursor of claim 1, wherein X is a hydride, ahydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substitutedhalocarbyl, or wherein two X groups together are a hydrocarbdiyl, ahalocarbdiyl, a substituted hydrocarbdiyl, or a substitutedhalocarbdiyl.
 9. The catalyst precursor of claim 1, wherein two X groupsare joined, and wherein the two X groups are independently selected fromthe group consisting of methylidene, ethylidene, propylidene,tetramethylene, pentamethylene, hexamethylene, butadiene,methylbutadiene, dimethylbutadiene, pentadiene, methylpentadiene,dimethylpentadiene, hexadiene, methylhexadiene, and dimethylhexadiene.10. The catalyst precursor of claim 2, wherein M comprises one or moreof cobalt, iron or manganese.
 11. The catalyst precursor of claim 2,wherein X is a hydride, a hydrocarbyl, a substituted hydrocarbyl, ahalocarbyl, a substituted halocarbyl, or wherein two X groups togetherare a hydrocarbdiyl, a halocarbdiyl, a substituted hydrocarbdiyl, or asubstituted halocarbdiyl.
 12. The catalyst precursor of claim 2, whereintwo X groups are joined, and wherein the two X groups are independentlyselected from the group consisting of methylidene, ethylidene,propylidene, tetramethylene, pentamethylene, hexamethylene, butadiene,methylbutadiene, dimethylbutadiene, pentadiene, methylpentadiene,dimethylpentadiene, hexadiene, methylhexadiene, and dimethylhexadiene.13. The catalyst precursor of claim 3, wherein M comprises one or moreof cobalt, iron or manganese.
 14. The catalyst precursor of claim 3,wherein X is a hydride, a hydrocarbyl, a substituted hydrocarbyl, ahalocarbyl, a substituted halocarbyl, or wherein two X groups togetherare a hydrocarbdiyl, a halocarbdiyl, a substituted hydrocarbdiyl, or asubstituted halocarbdiyl.
 15. The catalyst precursor of claim 3, whereintwo X groups are joined, and wherein the two X groups are independentlyselected from the group consisting of methylidene, ethylidene,propylidene, tetramethylene, pentamethylene, hexamethylene, butadiene,methylbutadiene, dimethylbutadiene, pentadiene, methylpentadiene,dimethylpentadiene, hexadiene, methylhexadiene, and dimethylhexadiene.16. The catalyst precursor of claim 4, wherein M comprises one or moreof cobalt, iron or manganese.
 17. The catalyst precursor of claim 4,wherein X is a hydride, a hydrocarbyl, a substituted hydrocarbyl, ahalocarbyl, a substituted halocarbyl, or wherein two X groups togetherare a hydrocarbdiyl, a halocarbdiyl, a substituted hydrocarbdiyl, or asubstituted halocarbdiyl.
 18. The catalyst precursor of claim 4, whereintwo X groups are joined, and wherein the two X groups are independentlyselected from the group consisting of methylidene, ethylidene,propylidene, tetramethylene, pentamethylene, hexamethylene, butadiene,methylbutadiene, dimethylbutadiene, pentadiene, methylpentadiene,dimethylpentadiene, hexadiene, methylhexadiene, and dimethylhexadiene.19. The catalyst precursor of claim 5, wherein M comprises one or moreof cobalt, iron or manganese.
 20. The catalyst precursor of claim 5,wherein X is a hydride, a hydrocarbyl, a substituted hydrocarbyl, ahalocarbyl, a substituted halocarbyl, or wherein two X groups togetherare a hydrocarbdiyl, a halocarbdiyl, a substituted hydrocarbdiyl, or asubstituted halocarbdiyl.
 21. The catalyst precursor of claim 5, whereintwo X groups are joined, and wherein the two X groups are independentlyselected from the group consisting of methylidene, ethylidene,propylidene, tetramethylene, pentamethylene, hexamethylene, butadiene,methylbutadiene, dimethylbutadiene, pentadiene, methylpentadiene,dimethylpentadiene, hexadiene, methylhexadiene, and dimethylhexadiene.22. The catalyst precursor of claim 6, wherein M comprises one or moreof cobalt, iron or manganese.
 23. The catalyst precursor of claim 6,wherein X is a hydride, a hydrocarbyl, a substituted hydrocarbyl, ahalocarbyl, a substituted halocarbyl, or wherein two X groups togetherare a hydrocarbdiyl, a halocarbdiyl, a substituted hydrocarbdiyl, or asubstituted halocarbdiyl.
 24. The catalyst precursor of claim 6, whereintwo X groups are joined, and wherein the two X groups are independentlyselected from the group consisting of methylidene, ethylidene,propylidene, tetramethylene, pentamethylene, hexamethylene, butadiene,methylbutadiene, dimethylbutadiene, pentadiene, methylpentadiene,dimethylpentadiene, hexadiene, methylhexadiene, and dimethylhexadiene.25. The catalyst precursor of claim 1, wherein R⁶ is selected from thegroup consisting of propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, octacosyl, nonacosyl,triacontyl, cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl,cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl,dimethylphenyl, trimethylphenyl, methylphenyl, ethylphenyl,diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl,tripropylphenyl, methylethylphenyl, dibutylphenyl, and butylphenyl. 26.The catalyst precursor of claim 1, wherein R⁶ is selected from the groupconsisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.
 27. The catalyst precursor of claim 2, wherein R⁶ isselected from the group consisting of propyl, butyl, pentyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, octacosyl,nonacosyl, triacontyl, cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl,cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl,dimethylphenyl, trimethylphenyl, methylphenyl, ethylphenyl,diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl,tripropylphenyl, methylethylphenyl, dibutylphenyl, and butylphenyl. 28.The catalyst precursor of claim 2, wherein R⁶ is selected from the groupconsisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.
 29. The catalyst precursor of claim 3, wherein R⁶ isselected from the group consisting of propyl, butyl, pentyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, octacosyl,nonacosyl, triacontyl, cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl,cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl,dimethylphenyl, trimethylphenyl, methylphenyl, ethylphenyl,diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl,tripropylphenyl, methylethylphenyl, dibutylphenyl, and butylphenyl. 30.The catalyst precursor of claim 3, wherein R⁶ is selected from the groupconsisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.
 31. The catalyst precursor of claim 4, wherein R⁶ isselected from the group consisting of propyl, butyl, pentyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, octacosyl,nonacosyl, triacontyl, cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl,cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl,dimethylphenyl, trimethylphenyl, methylphenyl, ethylphenyl,diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl,tripropylphenyl, methylethylphenyl, dibutylphenyl, and butylphenyl. 32.The catalyst precursor of claim 4, wherein R⁶ is selected from the groupconsisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.
 33. The catalyst precursor of claim 5, wherein R⁶ isselected from the group consisting of propyl, butyl, pentyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, octacosyl,nonacosyl, triacontyl, cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl,cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl,dimethylphenyl, trimethylphenyl, methylphenyl, ethylphenyl,diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl,tripropylphenyl, methylethylphenyl, dibutylphenyl, and butylphenyl. 34.The catalyst precursor of claim 5, wherein R⁶ is selected from the groupconsisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.
 35. The catalyst precursor of claim 6, wherein R⁶ isselected from the group consisting of propyl, butyl, pentyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, octacosyl,nonacosyl, triacontyl, cyclohexyl, cyclopentyl, cycloheptyl, cyclooctyl,cyclodecyl, cyclododecyl, naphthyl, phenyl, tolyl, benzyl, phenethyl,dimethylphenyl, trimethylphenyl, methylphenyl, ethylphenyl,diethylphenyl, triethylphenyl, propylphenyl, dipropylphenyl,tripropylphenyl, methylethylphenyl, dibutylphenyl, and butylphenyl. 36.The catalyst precursor of claim 6, wherein R⁶ is selected from the groupconsisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.
 37. The catalyst precursor of claim 1, wherein M comprisesone or more of cobalt, iron or manganese and R⁶ is selected from thegroup consisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.
 38. The catalyst precursor of claim 2, wherein M comprisesone or more of cobalt, iron or manganese and R⁶ is selected from thegroup consisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.
 39. The catalyst precursor of claim 3, wherein M comprisesone or more of cobalt, iron or manganese and R⁶ is selected from thegroup consisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.
 40. The catalyst precursor of claim 4, wherein M comprisesone or more of cobalt, iron or manganese and R⁶ is selected from thegroup consisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.
 41. The catalyst precursor of claim 5, wherein M comprisesone or more of cobalt, iron or manganese and R⁶ is selected from thegroup consisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.
 42. The catalyst precursor of claim 6, wherein M comprisesone or more of cobalt, iron or manganese and R⁶ is selected from thegroup consisting of phenyl, phenethyl, dimethylphenyl, trimethylphenyl,methylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, propylphenyl,dipropylphenyl, tripropylphenyl, methylethylphenyl, dibutylphenyl, andbutylphenyl.